Electrochemical

Impedance Spectroscopy
Library

Cdc

Rt
∆O ∆R
ZO ZR

ER@SE

December 28, 2003

ER@SE/December 28, 2003 2
Contents

1 Reactions involving soluble species only 5

1.1 Redox reaction (E) . . . . . . . . . . . . . . . . . . . . . . . . . . 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
1.1.5 RDE (diffusion-convection) . . . . . . . . . . . . . . . . 6
1.1.6 Warburg conditions (semi-infinite linear diffusion) . . . 7
1.2 EE reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.2 Kinetic equations, without
coupled homogeneous reactions . . . . . . . . . . . . . . 8
1.2.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 8
1.2.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 9

2 Reactions involving one adsorbate 11

2.1 Electroadsorption reaction (EAR) . . . . . . . . . . . . . . . . . . 11
2.1.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 11
2.1.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 12
2.1.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 12
2.2 Dissolution-passivation reaction . . . . . . . . . . . . . . . . . . . 12
2.2.1 Mechanism [7] . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 12
2.2.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 13
2.2.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 13
2.3 Volmer-Heyrovský (V-H) reaction . . . . . . . . . . . . . . . . . . 14
2.3.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 14
2.3.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 15
2.3.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 15
2.4 Volmer-Tafel (V-T) reaction . . . . . . . . . . . . . . . . . . . . . 16
2.4.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.4.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 16
2.4.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 16
2.4.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 17
2.5 Volmer-Heyrovský-Tafel (V-H-T) reaction . . . . . . . . . . . . . 17
2.5.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 17

3
 2.5.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 18
2.5.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 18
2.5.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 19

3 Reactions involving two adsorbates 21

3.1 Volmer-Heyrovský with chemical desorption . . . . . . . . . . . . 21
3.1.1 Mechanism [6, 3, 4] . . . . . . . . . . . . . . . . . . . . . 21
3.1.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 21
3.1.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 22
3.1.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 22
3.2 Schuhmann dissolution-passivation
reaction # 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.1 Mechanism [7] . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 23
3.2.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 23
3.2.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 24

4 Reactions involving both adsorbed and soluble species 25

4.1 Electroadsorption reaction (EAR) with
limitation by mass transport . . . . . . . . . . . . . . . . . . . . 25
4.1.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 25
4.1.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 25
4.1.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 26
4.1.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 26
4.2 Electrosorption-desorption reaction . . . . . . . . . . . . . . . . . 26
4.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 26
4.2.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 27
4.2.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 27
4.2.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 28
4.3 (V-H) reaction with mass transport limitation . . . . . . . . . . . 28
4.3.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.3.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 28
4.3.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 29
4.3.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 30
4.4 Copper dissolution in HCl . . . . . . . . . . . . . . . . . . . . . . 31
4.4.1 Mechanism [5, 1, 2] . . . . . . . . . . . . . . . . . . . . . 31
4.4.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 31
4.4.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 32
4.4.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 32
4.5 (V-T) reaction with mass transfer limitation . . . . . . . . . . . . 33
4.5.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.5.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . 33
4.5.3 Steady-state conditions . . . . . . . . . . . . . . . . . . 34
4.5.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . 35

ER@SE/December 28, 2003 4

Chapter 1

Reactions involving soluble

species only

1.1 Redox reaction (E)

1.1.1 Mechanism
K
O + e ←→
r
R
Ko

Kr = kr exp (−αr f E) = k exp (−αr f (E − E ◦ ))

o

Ko = ko exp (αo f E) = k o exp (αo f (E − E ◦ )) , f = F/(R T ), αo + αr = 1

1.1.2 Kinetic equations

Transformation rates
vO (t) = −v(t), vR (t) = v(t)

Mass balance equations

Flux of soluble species : JO (0, t) = vO (t), JR (0, t) = vR (t)

Current density vs. reaction rate

if (t) = −F v(t)

Reaction rate
v(t) = −R(0, t) Ko(t) + O(0, t) Kr (t)

1.1.3 Steady-state conditions

Steady-state equations
Soluble species

JO (0) = − (O∗ − O(0)) mO , JR (0) = − (R∗ − R(0)) mR

5
Steady-state solutions
Soluble species

R∗ + Kr (R∗ /mO + O∗ /mR ) O∗ + Ko (R∗ /mO + O∗ /mR )

R(0) = , O(0) =
1 + Ko /mR + Kr /mO 1 + Ko /mR + Kr /mO

Current density
F (Ko R∗ − Kr O∗ )
if =
1 + Ko /mR + Kr /mO

1.1.4 Faradaic impedance

1.1.5 RDE (diffusion-convection)
Faradaic impedance
Faradaic impedance

Zf (s) = Rct + ZO (s) + ZR (s)

1 + Kr MO (s) + Ko MR (s)
Zf (s) =
f F (R(0) Ko αo + O(0) Kr αr )

Charge transfer resistance

1
Rct =
f F (R(0) Ko αo + O(0) Kr αr )

∂v
Concentration impedances (with ∂X v = )
∂X
∂O v MO (s)
ZO = − = Kr Rct MO (s)
∂E v
∂R v MR (s)
ZR = = Ko Rct MR (s)
∂ v
√E √
1 th τdO s 1 th τdR s
MO (s) = √ , MR (s) = √
mO τdO s mR τdR s

Equivalent circuit (Fig. 1.1)

Cdc

Rt
∆O ∆R
ZO ZR

Figure 1.1: Equivalent circuit for the impedance of redox reactions (RDE).

ER@SE/December 28, 2003 6

1.1.6 Warburg conditions (semi-infinite linear diffusion)
Faradaic impedance

Zf (s) = Rct + ZO (s) + ZR (s)

only at the equilibrium potential:

1 O∗
E = Eeq = E ◦ + ln ∗
f R

1 + Kr MO (s) + Ko MR (s)
Zf (s) =
f F (R∗ Ko αo + O∗ Kr αr )
Charge transfer resistance
1
Rct =
f F (R∗ Ko αo + O∗ Kr αr )

Concentration impedances

ZO (s) = Kr Rct MO (s), ZR (s) = Ko Rct MR (s)

1 1
MO (s) = √ , MR (s) = √
s DO s DR

Equivalent circuit (Fig. 1.2)

Cdc

Rt
O R
ZO ZR

Figure 1.2: Equivalent circuit for the impedance of redox reactions: Warburg condi-
tions.

ER@SE/December 28, 2003 7

1.2 EE reaction
1.2.1 Mechanism

X + e−
K
R ←→
o1

Kr1

X ←→ O + e−
Ko2
Kr2

Ko1 = ko1 exp (αo1 f E) = k1o exp (αo1 f (E − E1o ))

Kr1 = kr1 exp (−αr1 f E) = k1o exp (−αr1 f (E − E1o )) , αo1 + αr1 = 1
Ko2 = ko2 exp (αo2 f E) = k2o exp (αo2 f (E − E2o ))
Kr2 = kr2 exp (−αr2 f E) = k2o exp (−αr2 f (E − E2o )) , αo2 + αr2 = 1

1.2.2 Kinetic equations, without

coupled homogeneous reactions

Transformation rates
vR (t) = −v1 (t), vX (t) = v1 (t) − v2 (t), vO (t) = v2 (t)

Mass balance equations

Flux of soluble species

JR (0, t) = vR (t), JX (0, t) = vX (t), JO (0, t) = vO (t)

Current density vs. step rates

if (t) = F (v1 (t) + v2 (t))

Step rates
v1 (t) = R(0, t) Ko1 (t) − X(0, t) Kr1 (t), v2 (t) = X(0, t) Ko2 (t) − O(0, t) Kr2 (t)

1.2.3 Steady-state conditions

Steady-state equations
JR (0) = − (R∗ − R(0)) mR , JX (0) = − (X ∗ − X(0)) mX , JO (0) = − (O∗ − O(0)) mO

Steady-state solutions
Soluble species


R∗ Kr2 X ∗ Kr1 X ∗ Kr1 Kr2
R(0) = R∗ + + + +
mO mR mO mR

R∗ Ko2 R∗ Kr1 R∗ Kr1 Kr2 O∗ Kr1 Kr2
+ + + /
mX mX mO mX mR mX


Kr2 Ko1 Ko1 Kr2 Ko2 Kr1 Kr1 Kr2 Ko1 Ko2
1+ + + + + + +
mO mR mO mR mX mX mO mX mR mX

ER@SE/December 28, 2003 8



X ∗ Kr2 X ∗ Ko1 X ∗ Ko1 Kr2
X(0) = X ∗ + + + +
mO mR mO mR

R∗ Ko1 O∗ Kr2 R∗ Ko1 Kr2 O∗ Ko1 Kr2
+ + + /
mX mX mO mX mR mX


Kr2 Ko1 Ko1 Kr2 Ko2 Kr1 Kr1 Kr2 Ko1 Ko2
1+ + + + + + +
mO mR mO mR mX mX mO mX mR mX

X ∗ Ko2 O∗ Ko1 X ∗ Ko1 Ko2
O(0) = O∗ + + + +
mO mR mO mR

O∗ Ko2 O∗ Kr1 R∗ Ko1 Ko2 O∗ Ko1 Ko2
+ + + /
mX mX mO mX mR mX


Kr2 Ko1 Ko1 Kr2 Ko2 Kr1 Kr1 Kr2 Ko1 Ko2
1+ + + + + + +
mO mR mO mR mX mX mO mX mR mX
Current density


Ko1 Ko2 X ∗ Ko1 Kr2 R∗ 2 Ko1 Ko2 R∗
if = Ko1 R∗ + Ko2 X ∗ + + + −
mR mO mX

Kr1 Kr2 X ∗ Ko1 Kr2 O∗ 2 Kr1 Kr2 O∗
Kr1 X ∗ − Kr2 O∗ − − − /
mO mR mX


Kr2 Ko1 Ko1 Kr2 Ko2 Kr1 Kr1 Kr2 Ko1 Ko2
1+ + + + + + +
mO mR mO mR mX mX mO mX mR mX

1.2.4 Faradaic impedance

Faradaic impedance

Zf (s) = Rct + ZO (s) + ZR (s) + ZX (s)

Zf (s) = (1 + Ko1 MO (s)) (1 + Kr2 MR (s)) + (Ko2 (1 + Ko1 MO (s)) + Kr1 (1 + Kr2 MR (s))) MX (s)/
(f F (X(0) Kr1 αr1 (1 + Kr2 MR (s) + 2 Ko2 MX (s))
+X(0) Ko2 αo2 (1 + 2 Kr1 MX (s)) + R(0) Kr2 αr2 (1 + 2 Kr1 MX (s))
+Ko1 ((X(0) Ko2 αo2 + R(0) Kr2 αr2 ) MO (s) + O(0) αo1 (1 + Kr2 MR (s) + 2 Ko2 MX (s)))))

Charge transfer resistance

1
Rct =
f F (O(0) Ko1 αo1 + X(0) (Ko2 αo2 + Kr1 αr1 ) + R(0) Kr2 αr2 )
Concentration impedances

ZO (s) = Rct Ko1 MO (s) (O(0) Ko1 αo1 (1 + Kr2 MR (s) + Ko2 MX (s))
+Kr1 (X(0) αr1 (1 + Kr2 MR (s)) + X(0) Ko2 (αo2 + αr1 ) MX (s) + R(0) Kr2 αr2 MX (s))) /
(X(0) Kr1 αr1 (1 + Kr2 MR (s) + 2 Ko2 MX (s))
+X(0) Ko2 αo2 (1 + 2 Kr1 MX (s)) + R(0) Kr2 αr2 (1 + 2 Kr1 MX (s))
+Ko1 ((X(0) Ko2 αo2 + R(0) Kr2 αr2 ) MO (s) + O(0) αo1 (1 + Kr2 MR (s) + 2 Ko2 MX (s))))

ER@SE/December 28, 2003 9

 ZX (s) = Rct (Ko2 − Kr1 ) MX (s) (X(0) Ko2 αo2 − X(0) Kr1 αr1 (1 + Kr2 MR (s))
+R(0) Kr2 αr2 + Ko1 ((X(0) Ko2 αo2 + R(0) Kr2 αr2 ) MO (s) − αo1 O(0) (1 + Kr2 MR (s)))) /
(X(0) Kr1 αr1 (1 + Kr2 MR (s) + 2 Ko2 MX (s))
+X(0) Ko2 αo2 (1 + 2 Kr1 MX (s)) + R(0) Kr2 αr2 (1 + 2 Kr1 MX (s))
+Ko1 ((X(0) Ko2 αo2 + R(0) Kr2 αr2 ) MO (s) + O(0) αo1 (1 + Kr2 MR (s) + 2 Ko2 MX (s))))

ZR (s) = Rct Kr2 MR (s) (R(0) Kr2 αr2 (1 + Ko1 MO (s) + Kr1 MX (s))
+Ko2 (X(0)αo2 + X(0)Kr1 (αo2 + αr1 ) MX (s) + Ko1 (X(0)αo2 MO (s) + O(0)αo1 MX (s)))) /
(X(0) Kr1 αr1 (1 + Kr2 MR (s) + 2 Ko2 MX (s))
+X(0) Ko2 αo2 (1 + 2 Kr1 MX (s)) + R(0) Kr2 αr2 (1 + 2 Kr1 MX (s))
+Ko1 ((X(0) Ko2 αo2 + R(0) Kr2 αr2 ) MO (s) + O(0) αo1 (1 + Kr2 MR (s) + 2 Ko2 MX (s))))

ER@SE/December 28, 2003 10

Chapter 2

Reactions involving one

adsorbate

2.1 Electroadsorption reaction (EAR)

2.1.1 Mechanism
A− + s ←→ A,s + e−
o K
Kr

2.1.2 Kinetic equations

No mass transport limitations, Langmuir isotherm

A− (0, t) ≈ A−∗ , Ko = ko A−∗ exp (αo f E) , Kr = kr exp (−αr f E)

Transformation rates

vA− (t) = −v1 (t), vs (t) = −v1 (t), vA (t) = v1 (t)

Mass balance equations

Rate of production of adsorbed species

dθs (t) vs (t) dθA (t) vA (t)

= , =
dt Γ dt Γ

Current density vs. reaction rate

if (t) = F v(t)

Reaction rate

v(t) = θs (t) Γ Ko (t) − θA (t) Γ Kr (t)

11
2.1.3 Steady-state conditions
Steady-state equations
Adsorbed species
dθs /dt = 0, θA + θs = 1

Steady-state solutions
Adsorbed species
Kr Ko
θs = , θA =
Ko + Kr Ko + Kr
Current density
if = 0

2.1.4 Faradaic impedance

Faradaic impedance
Zf (s) = Rct + ZA (s) + Zs (s)
s + Ko + Kr (Ko + Kr ) (s + Ko + Kr )
Zf (s) = =
f F Γ s (θs Ko αo + θA Kr αr ) f F s Γ Ko Kr
Charge transfer resistance
1 Ko + Kr
Rct = =
f F Γ (θs Ko αo + θA Kr αr ) f F Γ Ko Kr
Concentration impedances
Adsorbed species
Γ Kr Rct Ko + Kr Ko Rct Ko + Kr
ZA (s) = = , Zs (s) = =
s f F s Γ Ko s f F s Γ Kr

2.2 Dissolution-passivation reaction

2.2.1 Mechanism [7]
M2+ + s + 2 e−
K
M,s ←→
o1

Kr1

A− + s ←→ A,s + e−
K
o2

Kr2

2.2.2 Kinetic equations

No mass transport limitations, Langmuir isotherm
M 2+ (0, t) ≈ M 2+∗ , A− (0, t) ≈ A−∗
Ko1 = ko1 exp (2 αo1 f E) , Kr1 = kr1 M 2+∗ exp (−2 αr1 f E)
Ko2 = ko2 A−∗ exp (αo2 f E) , Kr2 = kr2 exp (−αr2 f E)

ER@SE/December 28, 2003 12

Transformation rates (vA stands for vA,s )
vs (t) = −v2 (t), vA (t) = v2 (t)

Mass balance equations

Rate of production of adsorbed species
dθs (t) vs (t) dθA (t) vA (t)
= , =
dt Γ dt Γ

Current density vs. step rates

if (t) = F (2 v1 (t) + v2 (t))

Step rates
v1 (t) = θs (t) Γ Ko1 (t) − θs (t) Γ Kr1 (t), v2 (t) = θs (t) Γ Ko2 (t) − θA (t) Γ Kr2 (t)

2.2.3 Steady-state conditions

Steady-state equations
Adsorbed species
dθs /dt = 0, θA + θs = 1

Steady-state solutions
Adsorbed species
Ko2 Kr2
θs = , θA =
Ko2 + Kr2 Ko2 + Kr2
Current density
2 F Γ (Ko1 − Kr1 ) Kr2
if =
Ko2 + Kr2

2.2.4 Faradaic impedance

Faradaic impedance
Faradaic impedance

Zf (s) = Rct + ZA (s) + Zs (s)

Zf (s) = (s + Ko2 + Kr2 ) /

(f F Γ (θs (Ko2 (s + 2 Kr1 ) αo2 + 2 Ko1 (2 (s + Ko2 + Kr2 ) αo1 − Ko2 αo2 ) +
4 Kr1 (s + Ko2 + Kr2 ) αr1 ) + θA (s − 2 Ko1 + 2 Kr1 ) Kr2 αr2 ))

Zf (s) =
(Ko2 + Kr2 ) (s + Ko2 + Kr2 )
f F Γ Kr2 (4 (s + Kr2 ) (Ko1 αo1 + Kr1 αr1 ) + Ko2 (s + Ko1 (−2 + 4 αo1 ) + Kr1 (2 + 4 αr1 )))

ER@SE/December 28, 2003 13

 Charge transfer resistance
1
Rct =
f F Γ (4 θs Ko1 αo1 + θs Ko2 αo2 + 4 θs Kr1 αr1 + θA Kr2 αr2 )

Ko2 + Kr2
Rct =
f F Γ Kr2 (Ko2 + 4 Ko1 αo1 + 4 Kr1 αr1 )
Concentration impedances

ZA (s) = Kr2 Rct (θs Ko2 αo2 + θA Kr2 αr2 )/

(θs (Ko2 (s + 2 Kr1 ) αo2 + 2 Ko1 (2 (s + Ko2 + Kr2 ) αo1 − Ko2 αo2 ) +
4 Kr1 (s + Ko2 + Kr2 ) αr1 ) + θA (s − 2 Ko1 + 2 Kr1 ) Kr2 αr2 )

Ko2 Kr2 Rct

ZA (s) =
4 (s + Kr2 ) (Ko1 αo1 + Kr1 αr1 ) + Ko2 (s + Ko1 (−2 + 4 αo1 ) + Kr1 (2 + 4 αr1 ))

Zs (s) = −(2 Ko1 + Ko2 − 2 Kr1 ) Rct (θs Ko2 αo2 + θA Kr2 αr2 )/
(θs (−4 Ko1 (s + Ko2 + Kr2 ) αo1 − Ko2 (s − 2 Ko1 + 2 Kr1 ) αo2 −
4 Kr1 (s + Ko2 + Kr2 ) αr1 ) − θA (s − 2 Ko1 + 2 Kr1 ) Kr2 αr2 )

Ko2 (2 Ko1 + Ko2 − 2 Kr1 ) Rct

Zs (s) =
4 (s + Kr2 ) (Ko1 αo1 + Kr1 αr1 ) + Ko2 (s + Ko1 (−2 + 4 αo1 ) + Kr1 (2 + 4 αr1 ))

2.3 Volmer-Heyrovský (V-H) reaction

2.3.1 Mechanism
A+ + s + e− ←→
r1 K
A,s
Ko1

A+ + A,s + e− ←→
r2 K
A2 + s
Ko2

2.3.2 Kinetic equations

No mass transport limitations, Langmuir isotherm

A+ (0, t) ≈ A+∗ , A2 (0, t) ≈ A∗2

Kr1 = kr1 A+∗ exp (−αr1 f E) , Ko1 = ko1 exp (αo1 f E)

Kr2 = kr2 A+∗ exp (−αr2 f E) , Ko2 = ko2 A∗2 exp (αo2 f E)

Transformation rates
vs (t) = −v1 (t) + v2 (t), vA (t) = v1 (t) − v2 (t)

ER@SE/December 28, 2003 14

Mass balance equations
Rate of production of adsorbed species

dθs (t) vs (t) dθA (t) vA (t)

= , =
dt Γ dt Γ

Current density vs. step rates

if (t) = −F (v1 (t) + v2 (t))

Step rates

v1 (t) = −θA (t) Γ Ko1 (t) + θs (t) Γ Kr1 (t), v2 (t) = −θs (t) Γ Ko2 (t) + θA (t) Γ Kr2 (t)

2.3.3 Steady-state conditions

Steady-state equations
Adsorbed species
dθs /dt = 0, θA + θs = 1

Steady-state solutions
Adsorbed species

Ko1 + Kr2 Ko2 + Kr1

θs = , θA =
Ko1 + Ko2 + Kr1 + Kr2 Ko1 + Ko2 + Kr1 + Kr2

Current density
2 F Γ (Ko1 Ko2 − Kr1 Kr2 )
if =
Ko1 + Ko2 + Kr1 + Kr2

2.3.4 Faradaic impedance

Faradaic impedance
Faradaic impedance

Zf (s) = Rct + ZA (s) + Zs (s)

Charge transfer resistance

1
Rct =
f F Γ (θA Ko1 αo1 + θs Ko2 αo2 + θs Kr1 αr1 + θA Kr2 αr2 )

Concentration impedances

ZA (s) = (Ko1 − Kr2 ) Rct (θA Ko1 αo1 − θs Ko2 αo2 + θs Kr1 αr1 − θA Kr2 αr2 )/
(θs Ko2 (s + 2 Kr1 ) αo2 + θs Kr1 (s + 2 Ko2 + 2 Kr2 ) αr1 + θA (s + 2 Kr1 ) Kr2 αr2 +
Ko1 (θA (s + 2 Ko2 + 2 Kr2 ) αo1 + 2 (θs Ko2 αo2 + θA Kr2 αr2 )))

ER@SE/December 28, 2003 15

 Zs (s) = (Ko2 − Kr1 ) Rct (− θA Ko1 αo1 + θs Ko2 αo2 − θs Kr1 αr1 + θA Kr2 αr2 )/
(θs Ko2 (s + 2 Kr1 ) αo2 + θs Kr1 (s + 2 Ko2 + 2 Kr2 ) αr1 + θA (s + 2 Kr1 ) Kr2 αr2 +
Ko1 (θA (s + 2 Ko2 + 2 Kr2 ) αo1 + 2 (θs Ko2 αo2 + θA Kr2 αr2 )))

2.4 Volmer-Tafel (V-T) reaction

2.4.1 Mechanism
A+ + s + e− ←→
r1 K
A,s
Ko1

k
2 A,s ←→
d2
A2 + 2 s
kg2

2.4.2 Kinetic equations

No mass transport limitations, Langmuir isotherm

A+ (0, t) ≈ A+∗ , A2 (0, t) ≈ A∗2


Kr1 = kr1 A+∗ exp (−αr1 f E) , Ko1 = ko1 exp (αo1 f E) , kg2 = kg2 A∗2

Transformation rates

vs (t) = −v1 (t) + 2 v2 (t), vA (t) = v1 (t) − 2 v2 (t)

Mass balance equations

Rate of production of adsorbed species

dθs (t) vs (t) dθA (t) vA (t)

= , =
dt Γ dt Γ

Current density vs. step rates

if (t) = −F v1 (t)

Step rates
2 2
v1 (t) = −θA (t) Γ Ko1 (t) + θs (t) Γ Kr1 (t), v2 (t) = θA (t) Γ2 kd2 − θs (t) Γ2 kg2

2.4.3 Steady-state conditions

Steady-state equations
Adsorbed species
dθs /dt = 0, θA + θs = 1

ER@SE/December 28, 2003 16

Steady-state solutions

Adsorbed species

 
2
− 4 Γ kg2 + Ko1 + Kr1 − 8 Γ kg2 Ko1 + 8 Γ kd2 (2 Γ kg2 + Kr1 ) + (Ko1 + Kr1 )
θA =
4 Γ (kd2 − kg2 )

Current density

F   
2
if = − 4 Γ kg2 Ko1 + 4 Γ kd2 Kr1 + (Ko1 + Kr1 ) +
4 (kd2 − kg2 )
 
2
(Ko1 + Kr1 ) 8 Γ kg2 Ko1 + 8 Γ kd2 (2 Γ kg2 + Kr1 ) + (Ko1 + Kr1 )

2.4.4 Faradaic impedance

Faradaic impedance

Faradaic impedance

Zf (s) = Rct + ZA (s) + Zs (s)

s + 4 θA Γ kd2 + 4 θs Γ kg2 + Ko1 + Kr1

Zf (s) =
F f Γ (s + 4 θA Γ kd2 + 4 θs Γ kg2 ) (θA Ko1 αo1 + θs Kr1 αr1 )
Charge transfer resistance

1
Rct =
f F Γ (θA Ko1 αo1 + θs Kr1 αr1 )

Concentration impedances

Ko1 Rct Kr1 Rct

ZA (s) = , Zs (s) =
s + 4 θA Γ kd2 + 4 θs Γ kg2 s + 4 θA Γ kd2 + 4 θs Γ kg2

2.5 Volmer-Heyrovský-Tafel (V-H-T) reaction

2.5.1 Mechanism
A+ + s + e− ←→
r1K
A,s
Ko1

A+ + A,s + e− ←→
r2K
A2 + s
Ko2

k
2 A,s ←→
d3
A2 + 2 s
kg3

ER@SE/December 28, 2003 17

2.5.2 Kinetic equations
No mass transport limitations, Langmuir isotherm
A+ (0, t) ≈ A+∗ , A2 (0, t) ≈ A∗2
Kr1 = kr1 A+∗ exp (−αr1 f E) , Ko1 = ko1 exp (αo1 f E)
Kr2 = kr2 A+∗ exp (−αr2 f E) , Ko2 = ko2 A∗2 exp (αo2 f E) , kg3 = kg3

A∗2

Transformation rates
vs (t) = −v1 (t) + v2 (t) + 2 v3 (t), vA (t) = v1 (t) − v2 (t) − 2 v3 (t)

Mass balance equations

Rate of production of adsorbed species
dθs (t) vs (t) dθA (t) vA (t)
= , =
dt Γ dt Γ

Current density vs. step rates

if (t) = −F (v1 (t) + v2 (t))

Step rates
v1 (t) = −θA (t) Γ Ko1 (t) + θs (t) Γ Kr1 (t)
v2 (t) = −θs (t) Γ Ko2 (t) + θA (t) Γ Kr2 (t)
v3 (t) = θA (t)2 Γ2 kd3 − θs (t)2 Γ2 kg3

2.5.3 Steady-state conditions

Steady-state equations
Adsorbed species
dθs /dt = 0, θA + θs = 1

Steady-state solutions
Adsorbed species
1
θA = (4 Γ kg3 + Ko1 + Ko2 + Kr1 + Kr2 −
4 Γ (kg3 − kd3 )
 
2
8 Γ (kd3 − kg3 ) (2 Γ kg3 + Ko2 + Kr1 ) + (4 Γ kg3 + Ko1 + Ko2 + Kr1 + Kr2 )

Current density
F 
2
if = 4 Γ kd3 (Ko2 − Kr1 ) − (Ko1 + Kr1 ) + 4 Γ kg3 (−Ko1 + Kr2 ) +
4 (kd3 − kg3 )
2
(Ko2 + Kr2 ) + (Ko1 − Ko2 + Kr1 − Kr2 )
 
2
× 8 Γ (kd3 − kg3 ) (2 Γ kg3 + Ko2 + Kr1 ) + (4 Γ kg3 + Ko1 + Ko2 + Kr1 + Kr2 )

ER@SE/December 28, 2003 18

2.5.4 Faradaic impedance
Faradaic impedance

Zf (s) = Rct + ZA (s) + Zs (s)

Zf (s) = (s + 4 θA Γ kd3 + 4 θs Γ kg3 + Ko1 + Ko2 + Kr1 + Kr2 ) /

(f F Γ (θs Ko2 (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Kr1 ) αo2
+θs Kr1 (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Ko2 + 2 Kr2 ) αr1
+θA (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Kr1 ) Kr2 αr2
+Ko1 (θA (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Ko2 + 2 Kr2 ) αo1 + 2 (θs Ko2 αo2 + θA Kr2 αr2 ))))

Charge transfer resistance

1
Rct =
f F Γ (θA Ko1 αo1 + θs Ko2 αo2 + θs Kr1 αr1 + θA Kr2 αr2 )

Concentration impedances

ZA (s) = (Ko1 − Kr2 ) Rct (θA Ko1 αo1 − θs Ko2 αo2 + θs Kr1 αr1 − θA Kr2 αr2 )/
(θs Ko2 (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Kr1 ) αo2
+θs Kr1 (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Ko2 + 2 Kr2 ) αr1
+θA (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Kr1 ) Kr2 αr2
+Ko1 (θA (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Ko2 + 2 Kr2 ) αo1 + 2 (θs Ko2 αo2 + θA Kr2 αr2 )))

Zs (s) = (Ko2 − Kr1 ) Rct (− θA Ko1 αo1 + θs Ko2 αo2 − θs Kr1 αr1 + θA Kr2 αr2 )/
(θs Ko2 (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Kr1 ) αo2
+θs Kr1 (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Ko2 + 2 Kr2 ) αr1
+θA (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Kr1 ) Kr2 αr2
+Ko1 (θA (s + 4 θA Γ kd3 + 4 θs Γ kg3 + 2 Ko2 + 2 Kr2 ) αo1 + 2 (θs Ko2 αo2 + θA Kr2 αr2 )))

ER@SE/December 28, 2003 19

ER@SE/December 28, 2003 20
Chapter 3

Reactions involving
two adsorbates

3.1 Volmer-Heyrovský with chemical desorption

3.1.1 Mechanism [6, 3, 4]

A+ + s + e− −→
r1 K
A,s

A+ + A,s + e− −→
r2 K
A2 ,s
k
A2 ,s −→
d3
A2 + s

3.1.2 Kinetic equations

No mass transfer limitations, Langmuir isotherm

A+ (0, t) ≈ A+∗

Kr1 = kr1 A+∗ exp (−αr1 f E) , Kr2 = kr2 A+∗ exp (−αr2 f E)

Transformation rates

vs (t) = −v1 (t) + v3 (t), vA (t) = v1 (t) − v2 (t), vA2 (t) = v2 (t) − v3 (t)

Mass balance equations

Rate of production of adsorbed species

dθs (t) vs (t) dθA (t) vA (t) dθA2 (t) vA (t)

= , = , = 2
dt Γ dt Γ dt Γ

Current density vs. step rates

if (t) = −F (v1 (t) + v2 (t))

21
Step rates
v1 (t) = θs (t) Γ Kr1 (t), v2 (t) = θA (t) Γ Kr2 (t), v3 (t) = θA2 (t) Γ kd3

3.1.3 Steady-state conditions

Steady-state equations
Adsorbed species

dθs /dt = 0, dθA /dt = 0, θA + θA2 + θs = 1

Steady-state solutions
Adsorbed species
kd3 Kr1 Kr1 Kr2
θA = , θ A2 =
Kr1 Kr2 + kd3 (Kr1 + Kr2 ) Kr1 Kr2 + kd3 (Kr1 + Kr2 )
Current density
−2 F Γ kd3 Kr1 Kr2
if =
Kr1 Kr2 + kd3 (Kr1 + Kr2 )

3.1.4 Faradaic impedance

Faradaic impedance

Zf (s) = Rct + ZA (s) + Zs (s)

Charge transfer resistance

1
Rct =
f F Γ (θs Kr1 αr1 + θA Kr2 αr2 )
Concentration impedances
Kr2 Rct (− (θs (s + kd3 ) Kr1 αr1 ) + θA (s + kd3 + Kr1 ) Kr2 αr2 )
ZA (s) =
θs (s + kd3 ) Kr1 (s + 2 Kr2 ) αr1 + θA (s (s + kd3 ) + (s + 2 kd3 ) Kr1 ) Kr2 αr2

Kr1 Rct (θs Kr1 (s + Kr2 ) αr1 − kd3 (−θs Kr1 αr1 + θA Kr2 αr2 ))
Zs (s) =
θs (s + kd3 ) Kr1 (s + 2 Kr2 ) αr1 + θA (s (s + kd3 ) + (s + 2 kd3 ) Kr1 ) Kr2 αr2

3.2 Schuhmann dissolution-passivation

reaction # 1
3.2.1 Mechanism [7]
K
M,s ←→
o1
X,s + 2 e
Kr1

K
X,s ←→
o2
Q,s + 2 e
Kr2

K
X,s + A −→
o3
X,s + B + 2 e

ER@SE/December 28, 2003 22

3.2.2 Kinetic equations
No mass transfer limitations, Langmuir isotherm

A(0, t) ≈ A∗

Ko1 = ko1 exp (2 αo1 f E) , Kr1 = kr1 exp (−2 αr1 f E)

Ko2 = ko2 exp (2 αo2 f E) , Kr2 = kr2 exp (−2 αr2 f E) , Ko3 = ko3 exp (2 αo3 f E)

Transformation rates

vs (t) = −v1 (t), vX (t) = v1 (t) − v2 (t), vQ (t) = v2 (t)

Mass balance equations

Rate of production of adsorbed species

dθs (t) vs (t) dθX (t) vX (t) dθQ (t) vQ (t)

= , = , =
dt Γ dt Γ dt Γ

Current density vs. step rates

if (t) = 2 F (v1 (t) + v2 (t) + v3 (t))

Step rates

v1 (t) = θs (t) Γ Ko1 (t) − θX (t) Γ Kr1 (t)

v2 (t) = θX (t) Γ Ko2 (t) − θQ (t) Γ Kr2 (t)

v3 (t) = θX (t) Γ Ko3 (t)

3.2.3 Steady-state conditions

Steady-state equations
Adsorbed species

dθs /dt = 0, dθX /dt = 0, θQ + θs + θX = 1

Steady-state solutions
Adsorbed species

Ko1 Ko2 Ko1 Kr2

θQ = , θX =
Kr1 Kr2 + Ko1 (Ko2 + Kr2 ) Kr1 Kr2 + Ko1 (Ko2 + Kr2 )

Current density

2 F Γ Ko1 Ko3 Kr2

if =
Kr1 Kr2 + Ko1 (Ko2 + Kr2 )

ER@SE/December 28, 2003 23

3.2.4 Faradaic impedance
Faradaic impedance

Zf (s) = Rct + ZQ (s) + Zs (s) + ZX (s)

Charge transfer resistance

1
Rct =
4 f F Γ (θs Ko1 αo1 + θX Ko2 αo2 + θX Ko3 αo3 + θX Kr1 αr1 + θQ Kr2 αr2 )

Concentration impedances

ZQ (s) = Kr2 Rct (Ko2 (θX (s + Kr1 ) αo2 + Ko1 (θs αo1 + θX αo2 ) +
θX Kr1 αr1 ) + θQ (s + Ko1 + Kr1 ) Kr2 αr2 ) /
 2
θX s Ko3 αo3 + θX s Ko3 Kr1 αo3 + θX s Ko3 Kr2 αo3 + θX Ko3 Kr1 Kr2 αo3 +
θX s2 Kr1 αr1 + θX s Ko3 Kr1 αr1 + θX s Kr1 Kr2 αr1 + θX Ko3 Kr1 Kr2 αr1 +
θX s Ko2 ((s − Ko3 + 2 Kr1 ) αo2 + Ko3 αo3 + 2 Kr1 αr1 ) +
θQ s2 Kr2 αr2 − θQ s Ko3 Kr2 αr2 + 2 θQ s Kr1 Kr2 αr2 +
Ko1 (θs (2 s Ko2 + (s + Ko3 ) (s + Kr2 )) αo1 + θX s Ko3 αo3 +
θX Ko3 Kr2 αo3 + θX Ko2 ((s − Ko3 ) αo2 + Ko3 αo3 ) + θQ s Kr2 αr2 − θQ Ko3 Kr2 αr2 ))

Zs (s) = Ko1 Rct (θs Ko1 (s + Ko2 + Kr2 ) αo1 +

Kr1 (θX Ko2 αo2 + θX (s + Ko2 + Kr2 ) αr1 + θQ Kr2 αr2 )) /
 2
θX s Ko3 αo3 + θX s Ko3 Kr1 αo3 + θX s Ko3 Kr2 αo3 + θX Ko3 Kr1 Kr2 αo3 +
θX s2 Kr1 αr1 + θX s Ko3 Kr1 αr1 + θX s Kr1 Kr2 αr1 + θX Ko3 Kr1 Kr2 αr1 +
θX s Ko2 ((s − Ko3 + 2 Kr1 ) αo2 + Ko3 αo3 + 2 Kr1 αr1 ) +
θQ s2 Kr2 αr2 − θQ s Ko3 Kr2 αr2 + 2 θQ s Kr1 Kr2 αr2 +
Ko1 (θs (2 s Ko2 + (s + Ko3 ) (s + Kr2 )) αo1 + θX s Ko3 αo3 +
θX Ko3 Kr2 αo3 + θX Ko2 ((s − Ko3 ) αo2 + Ko3 αo3 ) + θQ s Kr2 αr2 − θQ Ko3 Kr2 αr2 ))

ZX (s) = (Ko2 + Ko3 − Kr1 ) Rct (θX s Ko2 αo2 − θX Kr1 (s + Kr2 ) αr1 + θQ s Kr2 αr2 +
Ko1 (− (θs (s + Kr2 ) αo1 ) + θX Ko2 αo2 + θQ Kr2 αr2 )) /
(θX (s Ko2 ((s − Ko3 + 2 Kr1 ) αo2 + Ko3 αo3 + 2 Kr1 αr1 ) +
(s + Kr2 ) (Ko3 (s + Kr1 ) αo3 + (s + Ko3 ) Kr1 αr1 )) + θQ s (s − Ko3 + 2 Kr1 ) Kr2 αr2 +
Ko1 (θs (2 s Ko2 + (s + Ko3 ) (s + Kr2 )) αo1 + θX Ko2 (s − Ko3 ) αo2 +
θX Ko3 (s + Ko2 + Kr2 ) αo3 + θQ (s − Ko3 ) Kr2 αr2 ))

ER@SE/December 28, 2003 24

Chapter 4

Reactions involving
both adsorbed
and soluble species

4.1 Electroadsorption reaction (EAR) with

limitation by mass transport
4.1.1 Mechanism
A− + s ←→ A,s + e−
o K
Kr

4.1.2 Kinetic equations

Langmuir isotherm : Ko = ko exp (αo f E) , Kr = kr exp (−αr f E)

Transformation rates

vA− (t) = −v1 (t), vs (t) = −v1 (t), vA (t) = v1 (t)

Mass balance equations

Flux of soluble species

JA− (0, t) = vA− (t)

Rate of production of adsorbed species

dθs (t) vs (t) dθA (t) vA (t)

= , =
dt Γ dt Γ

Current density vs. reaction rate

if (t) = F v(t)

25
Reaction rate
v(t) = A− (0, t) θs (t) Γ Ko (t) − θA (t) Γ Kr (t)

4.1.3 Steady-state conditions

Steady-state equations
Soluble species
 
∗
JA− (0) = − A− − A− (0) mA−

Adsorbed species
dθs /dt = 0, θA + θs = 1

Steady-state solutions
Soluble species
A− (0) = A−∗
Adsorbed species
∗
Kr A− Ko
θs = − ∗ , θA = − ∗
A Ko + Kr A Ko + Kr
Current density
if = 0

4.1.4 Faradaic impedance

Faradaic impedance
Zf (s) = Rct + ZA− (s) + ZA (s) + Zs (s)
Charge transfer resistance
1
Rct =
f F Γ (A−∗ θs Ko αo + θA Kr αr )
Concentration impedances
Soluble species
√
1 th τA− s
ZA− (s) = θs Γ Ko Rct MA− (s), MA− (s) = √
m A− τA− s
Adsorbed species
A−∗ Ko Rct Γ Kr Rct
Zs (s) = , ZA (s) =
s s

4.2 Electrosorption-desorption reaction

4.2.1 Mechanism
A− + s ←→ A,s + e−
K
o1

Kr1
kd2
A,s −→ A + s

ER@SE/December 28, 2003 26

4.2.2 Kinetic equations
Langmuir isotherm: Ko1 = ko1 exp (αo1 f E) , Kr1 = kr1 exp (−αr1 f E)

Transformation rates
vA− (t) = −v1 (t), vs (t) = −v1 (t) + v2 (t), vA (t) = v1 (t) − v2 (t)

Mass balance equations

Flux of soluble species

JA− (0, t) = vA− (t)

Rate of production of adsorbed species

dθs (t) vs (t) dθA (t) vA (t)

= , =
dt Γ dt Γ

Current density vs. step rates

if (t) = F v1 (t)

Step rates
v1 (t) = A− (0, t) θs (t) Γ Ko1 (t) − θA (t) Γ Kr1 (t), v2 (t) = θA (t) Γ kd2

4.2.3 Steady-state conditions

Steady-state equations
Soluble species  
JA− (0) = − A−∗ − A− (0) mA−
Adsorbed species
dθs /dt = 0, θA + θs = 1

Steady-state solutions
Soluble species

1 
∗
A− (0) = A− Ko1 mA− − Kr1 mA− − kd2 (Γ Ko1 + mA− ) +
2 Ko1 mA−
 
− ∗ 2
4 Γ kd2 Ko1 (kd2 + Kr1 ) mA− + ((A Ko1 + Kr1 ) mA− + kd2 (−Γ Ko1 + mA− ))

Adsorbed species

1 
∗
θA = A− Ko1 mA− + Kr1 mA− + kd2 (Γ Ko1 + mA− ) −
2 Γ kd2 Ko1
 
− ∗ 2
4 Γ kd2 Ko1 (kd2 + Kr1 ) mA− + ((sA Ko1 + Kr1 ) mA− + kd2 (−Γ Ko1 + mA− ))

ER@SE/December 28, 2003 27

 Current density
F  − ∗ 
if = A Ko1 + Kr1 mA− + kd2 (Γ Ko1 + mA− ) −
2 Ko1

 ∗  2
−
4 Γ kd2 Ko1 (kd2 + Kr1 ) mA− + A Ko1 + Kr1 mA− + kd2 (−Γ Ko1 + mA− )

4.2.4 Faradaic impedance

Faradaic impedance
Zf (s) = Rct + ZA− (s) + ZA (s) + Zs (s)
s + kd2 + A− (0) Ko1 + Kr1 + θs Γ (s + kd2 ) Ko1 MA− (s)
Zf (s) =
f F Γ (s + kd2 ) (A− (0) θs Ko1 αo1 + θA Kr1 αr1 )
√
1 th τA− s
MA− (s) = √
m A− τA− s
Charge transfer resistance
1
Rct =
f F Γ (A− (0) θs Ko1 αo1 + θA Kr1 αr1 )
Concentration impedances
Soluble species
ZA− (s) = θs Γ Ko1 Rct MA− (s)
Adsorbed species
A− (0) Ko1 Rct Kr1 Rct
Zs (s) = , ZA (s) =
s + kd2 s + kd2

4.3 (V-H) reaction with mass transport limita-

tion
4.3.1 Mechanism
A+ + s + e− ←→
K
r1
A,s
Ko1

A+ + A,s + e− ←→
r2K
A2 + s
Ko2

4.3.2 Kinetic equations

Langmuir isotherm
Kr1 = kr1 exp (−αr1 f E) , Ko1 = ko1 exp (αo1 f E)
Kr2 = kr2 exp (−αr2 f E) , Ko2 = ko2 exp (αo2 f E)

ER@SE/December 28, 2003 28

Transformation rates
vA+ (t) = −v1 (t) − v2 (t), vs (t) = −v1 (t) + v2 (t), vA (t) = v1 (t) − v2 (t)

Mass balance equations

Flux of soluble species
JA+ (0, t) = vA+ (t), JA2 (0, t) = vA2 (t)
Rate of productions of adsorbed species
dθs (t) vs (t) dθA (t) vA (t)
= , =
dt Γ dt Γ

Current density vs. step rate

if (t) = −F (v1 (t) + v2 (t))

Step rates
v1 (t) = −θA (t) Γ Ko1 (t) + A+ (0, t) θs (t) Γ Kr1 (t)
v2 (t) = −A2 (0, t) θs (t) Γ Ko2 (t) + A+ (0, t) θA (t) Γ Kr2 (t)

4.3.3 Steady-state conditions

Steady-state equations
Soluble species
 
∗
JA+ (0) = − A+ − A+ (0) mA+ , JA2 (0) = − (A2 ∗ − A2 (0)) mA2

Adsorbed species
dθs /dt = 0, θA + θs = 1

Steady-state solution
Soluble species (1 )

A
0  mA

Kr1  Kr2  mA2 A   Ko1
 Ko2  mA2   Ko2
mA A   A2  mA2  
 
4  K K m  m 


K  K  A   K  A  K  m   K K 2 
o1 r2 A2 A r1 r2 o1 2 o2 A2 o1 o2

4 
Kr2 mA A   Ko1
2  Kr2  mA  mA2
Ko2
2 Kr1 mA2 A2  
Kr1 A   Ko1  mA   2 Ko1 Kr2 mA2  

Ko2 m2A  2
Kr1  Kr2  mA2 mA  4  Kr1 Kr2 mA2 

A2
0  Kr1 mA2
4  Kr2
mA A   2 A2  mA2   mA
mA A   4 A2  mA2  

mA  Ko1 Ko2 mA  mA2
4 Kr2 mA2 A2  
Kr2 A   Ko1  A2  Ko2  mA  
 
4  K K m  m 


K  K  A   K  A  K  m   K K 2  4 
K m  A  
o1 r2 A2 A r1 r2 o1 2 o2 A2 o1 o2 r2 A

Ko1
2  Kr2  mA  mA2
Ko2
2 Kr1 mA2 A2  
Kr1 A   Ko1  mA   2 Ko1 Kr2 mA2  

2 mA2
Ko2 m2A  2
Kr1  Kr2  mA2 mA  4  Kr1 Kr2 mA2 

Adsorbed species
Current density
1→ stands for =.

ER@SE/December 28, 2003 29

ΘA  4  Ko2 Kr1 mA2 A2   mA
 Ko2
2 Kr1 A   Ko1  

Kr1  Kr2  A   Ko1  A2  Ko2  mA2  
 
4  K K m  m 


K  K  A   K  A  K  m   K K 2 
o1 r2 A2 A r1 r2 o1 2 o2 A2 o1 o2

4 
Kr2 mA A   Ko1
2  Kr2  mA  mA2
Ko2
2 Kr1 mA2 A2  
Kr1 A   Ko1  mA   2 Ko1 Kr2 mA2  


4  Ko1 Kr2 mA2  2 Ko2
2  Kr1 mA2 A2   
Kr1 A  Ko1  mA 

 
i f  F mA 4  Kr1 Kr2 mA2 A  mA
 Ko1 Ko2 

Kr1  Kr2  A  Ko1  A2  Ko2  mA2  
 
4  K K m  m 


K  K  A   K  A  K  m   K K 2  4 
K m  A  
o1 r2 A2 A r1 r2 o1 2 o2 A2 o1 o2 r2 A

Ko1
2  Kr2  mA  mA2
Ko2
2 Kr1 mA2 A2  
Kr1 A   Ko1  mA   2 Ko1 Kr2 mA2  

Ko2 m2A  2
Kr1  Kr2  mA2 mA  4  Kr1 Kr2 mA2 

4.3.4 Faradaic impedance

Faradaic impedance

Zf (s) = Rct + ZA+ (s) + ZA2 (s) + ZA (s) + Zs (s)

Z f
s 
s  A
0
Kr1  Kr2   Ko1
2 ΘA  Kr2 MA
s  Θs  Ko2 MA2
s  1  Ko2
A2
0  Θs 
s  A
0 Kr1  MA2
s 
 MA
s
ΘA s Kr2  Kr1
Θs s  2 A
0
ΘA  Θs  Kr2  Θs Ko2
2 A2
0  Θs s  MA2
s 

f F 
A2
0 Θs Ko2
s  2 A
0 Kr1  Αo2  A
0 ΘA
s  2 A
0 Kr1  Kr2 Αr2 
A
0 Θs Kr1 Αr1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s 
Ko1
2
A2
0 Θs Ko2 Αo2  A
0 ΘA Kr2 Αr2   ΘA Αo1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s

√ √
1 th τA+ s 1 th τA2 s
M A+ = √ , MA2 = √
m A+ τA+ s m A2 τA2 s
Transfert resistance
1
Rct 






f F 
ΘA Ko1 Αo1  A2
0 Θs Ko2 Αo2  A
0 Θs Kr1 Αr1  A
0 ΘA Kr2 Αr2 

Concentration impedances
Soluble species

ZA
s  
Θs Kr1  ΘA Kr2  Rct MA
s

ZA2
s 

Θs  Ko2 Rct
A
0 Θs Kr1 Αr1
A2
0 Ko2  Kr2
A
0  ΘA s  MA
s  ΘA Ko1 Αo1
Kr2
ΘA s  MA
s  A
0 
A2
0 Ko2   A2
0 Θs Ko2 Αo2
s  Ko1  Kr1
A
0  Θs s  MA
s 
A
0 ΘA Kr2 Αr2
s  Ko1  Kr1
A
0  Θs s  MA
s MA2
s 


A2
0 Θs Ko2
s  2 A
0 Kr1  Αo2  A
0 ΘA
s  2 A
0 Kr1  Kr2 Αr2 
A
0 Θs Kr1 Αr1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s 
Ko1
2
A2
0 Θs Ko2 Αo2  A
0 ΘA Kr2 Αr2   ΘA Αo1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s

Adsorbed species

ER@SE/December 28, 2003 30

ZA
s 


Ko1  A
0 Kr2  Rct
A2
0 Θs Ko2 Αo2
2 Θs  Kr1 MA
s  1  A
0 ΘA Kr2 Αr2
2 Θs  Kr1 MA
s  1  ΘA Ko1 Αo1

2 ΘA  Kr2 MA
s  Θs  Ko2 MA2
s  1  A
0 Θs Kr1 Αr1
2 ΘA  Kr2 MA
s  Θs  Ko2 MA2
s  1 

A2
0 Θs Ko2
s  2 A
0 Kr1  Αo2  A
0 ΘA
s  2 A
0 Kr1  Kr2 Αr2 
A
0 Θs Kr1 Αr1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s 
Ko1
2
A2
0 Θs Ko2 Αo2  A
0 ΘA Kr2 Αr2   ΘA Αo1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s

Zs
s 


A2
0 Ko2  A
0 Kr1  Rct
A2
0 Θs Ko2 Αo2
2 Θs  Kr1 MA
s  1  A
0 ΘA Kr2 Αr2
2 Θs  Kr1 MA
s  1  ΘA Ko1
Αo1
2 ΘA  Kr2 MA
s  Θs  Ko2 MA2
s  1  A
0 Θs Kr1 Αr1
2 ΘA  Kr2 MA
s  Θs  Ko2 MA2
s  1 

A2
0 Θs Ko2
s  2 A
0 Kr1  Αo2  A
0 ΘA
s  2 A
0 Kr1  Kr2 Αr2 
A
0 Θs Kr1 Αr1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s 
Ko1
2
A2
0 Θs Ko2 Αo2  A
0 ΘA Kr2 Αr2   ΘA Αo1
s  2 A
0 Kr2  Ko2
2 A2
0  Θs s  MA2
s

4.4 Copper dissolution in HCl

4.4.1 Mechanism [5, 1, 2]
A− + M,s ←→ MA,s + e−
o1 K
Kr1

A− + MA,s ←→ MA−
d2 k
2 +s
kg2

4.4.2 Kinetic equations

Langmuir isotherm: Ko1 = ko1 exp (αo1 f E) , Kr1 = kr1 exp (−αr1 f E)

Transformation rates
vA− (t) = −v1 (t)−v2 (t), vMA2 − (t) = v2 (t), vs (t) = −v1 (t)+v2 (t), vMA (t) = v1 (t)−v2 (t)

Mass balance equations

Flux of soluble species

JA− (0, t) = vA− (t), JMA2 − (0, t) = vMA2 − (t)

Rate of production of adsorbed species

dθs (t) vs (t) dθMA (t) vM (t)

= , =
dt Γ dt Γ

Current density vs. step rates

if (t) = F v1 (t)

Step rates
v1 (t) = A− (0, t) θs (t) Γ Ko1 (t) − θMA (t) Γ Kr1 (t)
v2 (t) = A− (0, t) θMA (t) Γ kd2 − M A2 − (0, t) θs (t) Γ kg2

ER@SE/December 28, 2003 31

4.4.3 Steady-state conditions
Steady-state equations

Soluble species
   ∗

∗
JA− (0) = − A− − A− (0) mA− , JMA2 − (0) = − M A2 − − M A2 − (0) mMA2 −

Adsorbed species
dθs /dt = 0, θMA + θs = 1

Steady-state solutions
Soluble species

A
0 
mA

Kr1  A 
kd2  Ko1  mMA2   kg2
mA A    Kr1  MA2   mMA2   


 k K m  
4  k K 

k  K  A   MA   k  K  m   m  2 
g2 r1 A d2 r1 d2 o1 2 g2 r1 A MA2
4 
2  kd2 Kr1 
kd2 A   Kr1  mA  mMA2 
kg2
2 Ko1 mMA2  MA2   
Ko1 A   Kr1  mA  
2 kd2 Kr1 mMA2   
kg2 m2A  2
2  kd2 Ko1 
kd2  Ko1  mA  mMA2  

MA2 
0 
kg2
 Kr1  MA2   mMA2   m2A 



 k K m  
4  k K 

k  K  A   MA   k  K  m   m  2 
g2 r1 A d2 r1 d2 o1 2 g2 r1 A MA2
4 
2  kd2 Kr1 
kd2 A   Kr1  mA  mMA2 

kg2
2 Ko1 mMA2  MA2   
Ko1 A   Kr1  mA   2 kd2 Kr1 mMA2   mA 
mMA2 
4
2  kd2 Ko1 
kd2  Ko1  mA  mMA2  MA2    mA
4  kd2 Ko1 A  

kd2  Ko1  A   Kr1  mA  

4
2  kd2 Ko1 
kd2  Ko1  mA  m2MA2   2 kg2 m2A mMA2  

Adsorbed species

ΘMA 
 kg2
2 Ko1 A   Kr1  mA 
kg2
4  Ko1  mA  MA2   

kd2  Ko1  A   Kr1  mA  mMA2  


 k K m  
4  k K 

k  K  A   MA   k  K  m   m  2  4 
2  k K 
g2 r1 A d2 r1 d2 o1 2 g2 r1 A MA2 d2 r1

kd2 A   Kr1  mA  mMA2 
kg2
2 Ko1 mMA2  MA2   
Ko1 A   Kr1  mA   2 kd2 Kr1 mMA2   

4  kd2 Kr1 mMA2   2 kg2
2  Ko1 mMA2  MA2    
Ko1 A   Kr1  mA 

Current density

i f  
F mA
 kg2 Kr1 mA 
4  kd2 Ko1 A  

kd2  Ko1  A   MA2   kg2  Kr1  mA  mMA2  


 k K m  
4  k K 

k  K  A   MA   k  K  m   m  2 
g2 r1 A d2 r1 d2 o1 2 g2 r1 A MA2
4 
2  kd2 Kr1 
kd2 A   Kr1  mA  mMA2 

kg2
2 Ko1 mMA2  MA2   
Ko1 A   Kr1  mA   2 kd2 Kr1 mMA2   

2 kg2 m2A  4
2  kd2 Ko1 
kd2  Ko1  mA  mMA2  

4.4.4 Faradaic impedance

Faradaic impedance

Zf (s) = Rct + ZA− (s) + ZMA (s) + Zs (s)

ER@SE/December 28, 2003 32

Z f
s 
s  MA2 
0 k2  K1  K1
A
0  Θs 
s  2 MA2 
0 k2  MA
s 
k2
A
0  
2 A
0
ΘMA  Θs  K1  ΘMA
s  2 K1  MA
s 
Θs  k2
s  K1  K1
A
0  Θs s  MA
s MMA2 
s 

f F 
ΘMA K1 Α1  A
0 Θs K1 Α1 
s  k2
A
0  ΘMA s  MA
s  k2
MA2 
0  Θs s  MMA2 
s

1 th τA− s 1 th τMA− s
√

2
MA− = , MMA− =
m A− τA− s 2 mMA− τMA− s
2 2

Charge transfer resistance

1
Rct =
f F Γ (A− (0) θs Ko1 αo1 + θMA Kr1 αr1 )
Concentration impedances
Soluble species
  
θs Γ Ko1 Rct MA− (s) s + 2 A− (0) kd2 + kg2 2 M A2 − (0) + θs s Γ MMA2 − (s)
ZA− (s) =  
s + kd2 (A− (0) + θMA s Γ MA− (s)) + kg2 M A2 − (0) + θs s Γ MMA2 − (s)
Adsorbed species
 
Kr1 Rct 1 + 2 θMA Γ kd2 MA− (s) + θs Γ kg2 MMA2 − (s)
ZMA (s) =  
s + kd2 (A− (0) + θMA s Γ MA− (s)) + kg2 M A2 − (0) + θs s Γ MMA2 − (s)
 
A− (0) Ko1 Rct 1 + 2 θMA Γ kd2 MA− (s) + θs Γ kg2 MMA2 − (s)
Zs (s) =  
s + kd2 (A− (0) + θMA s Γ MA− (s)) + kg2 M A2 − (0) + θs s Γ MMA2 − (s)

4.5 (V-T) reaction with mass transfer limitation

4.5.1 Mechanism
A+ + s + e− ←→
r1 K
A,s
Ko1
k
2 A,s ←→
d2
A2 + 2 s
kg2

4.5.2 Kinetic equations

Langmuir isotherm: Kr1 = kr1 exp (−αr1 f E) , Ko1 = ko1 exp (αo1 f E)

Transformation rates
vA+ (t) = −v1 (t), vA2 (t) = v2 (t), vs (t) = −v1 (t) + 2 v2 (t), vA (t) = v1 (t) − 2 v2 (t)

Mass balance equations

Flux of soluble species
JA+ (0, t) = vA+ (t), JA2 (0, t) = vA2 (t)
Rate of production of adsorbed species,
dθs (t) vs (t) dθA (t) vA (t)
= , =
dt Γ dt Γ

ER@SE/December 28, 2003 33

Current density vs. step rates
if (t) = −F v1 (t)

Step rates
2 2
v1 (t) = −θA (t) Γ Ko1 (t)+A+ (0, t) θs (t) Γ Kr1 (t), v2 (t) = θA (t) Γ2 kd2 −A2 (0, t) θs (t) Γ2 kg2

4.5.3 Steady-state conditions

Steady-state equations
Soluble species
 ∗ 
JA+ (0) = − A+ − A+ (0) mA+ , JA2 (0) = (A2 ∗ − A2 (0)) mA2

Adsorbed species
dθA /dt = 0, θA + θs = 1

Steady-state solutions
Soluble species: A+ (0) and A2 (0) are solutions of cubic equations.
A+ (0):
   2  ∗  2
∗
2 kd2 A+ (0) Γ Kr1 + −A+ + A+ (0) mA+ mA2 = A+ − A+ (0) Ko1 + A+ (0) Kr1 mA+ mA2 +
   2   
∗ ∗
kg2 Γ Ko1 + A+ − A+ (0) mA+ A+ − A+ (0) mA+ + 2 A2 ∗ mA2

A2 (0):
  
∗
4 (A2 ∗ − A2 (0)) Kr1 mA2 2 Ko1 + A+ Kr1 mA+ + (A2 ∗ − A2 (0)) Kr1 mA2 +
2

  2
∗
kd2 2 (A2 ∗ − A2 (0)) mA+ mA2 + Γ Kr1 A+ mA+ + 2 (A2 ∗ − A2 (0)) mA2 =


 2  
∗ +∗ ∗ 2
m A+ 2
− (A2 − A2 (0)) Ko1 + A Kr1 mA2 + A2 (0) kg2 (Γ Ko1 + 2 (−A2 + A2 (0)) mA2 )

Adsorbed species: θA is solution of a cubic equation

2 A2 ∗ Γ kg2 mA2 (−mA+ + Γ Kr1 (−1 + θA )) (−1 + θA ) +

2
  
2 ∗
mA+ mA2 + Γ2 kg2 (−1 + θA ) A+ Kr1 (−1 + θA ) + Ko1 θA +
2 Γ kd2 mA2 θA 2 (mA+ + Kr1 (Γ − Γ θA )) = 0

Current density: if is solution of a cubic equation

 
∗
2 F if (2 Γ kd2 + Ko1 ) Kr1 mA+ if + A+ F mA+ mA2 +
   2
∗
if + 2 F Γ2 kd2 Kr1 2 if + A+ F mA+ mA2 +
   
F if 2 if kd2 + F Ko1 2 mA2 + kg2 (if − F Γ Ko1 ) (if − 2 A2 ∗ F mA2 ) = 0
2
m A+ 2

ER@SE/December 28, 2003 34

4.5.4 Faradaic impedance
Faradaic impedance

Zf (s) = Rct + ZA+ (s) + ZA (s) + Zs (s)

Z f
s 
s  Ko1  Kr1
A
0  Θs s  MA
s  4 ΘA  kd2
Θs  Kr1 MA
s  1 
Θs  kg2
4
Θs  Kr1 MA
s A2
0  A2
0  Θs 
s  Ko1  Kr1
A
0  Θs s  MA
s MA2
s 

f F 
ΘA Ko1 Αo1  A
0 Θs Kr1 Αr1 
s  4 ΘA  kd2  Θs  kg2
4 A2
0  Θs s  MA2
s
√ √
1 th τA+ s 1 th τA2 s
M A+ = √ , MA2 = √
m A+ τA+ s m A2 τA2 s
Charge transfer resistance
1
Rct =
f F Γ (θA Ko1 αo1 + A+ (0) θs Kr1 αr1 )

Concentration impedances Soluble species

ZA+ (s) = θs Γ Kr1 Rct MA+ (s)

Adsorbed species
 
Ko1 Rct 1 + θs 2 Γ2 kg2 MA2 (s)
ZA (s) =
s + 4 θA Γ kd2 + θs Γ kg2 (4 A2 (0) + θs s Γ MA2 (s))
 
A+ (0) Kr1 Rct 1 + θs 2 Γ2 kg2 MA2 (s)
Zs (s) =
s + 4 θA Γ kd2 + θs Γ kg2 (4 A2 (0) + θs s Γ MA2 (s))

ER@SE/December 28, 2003 35

ER@SE/December 28, 2003 36
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