Handbook of Electrochemical Impedance Spectroscopy

a 0.5 Im H log H 1 1 uc 1 0 d

0 0 0.5 Re H 0 log Im H b uc 1 H degrees 1

log uc log u

45

90 3 2 log Re H 1 0 2 log uc log u 0 f uc log H 1 1 0 2

1 Im H Re H ,

0 2 0 log u 2

2 90 45 H degrees 0

TRANSFER FUNCTIONS
ER@SE/LEPMI J.-P. Diard, B. Le Gorrec, C. Montella Hosted by Bio-Logic @ www.bio-logic.info

January 4, 2009

Contents
1 Graphs of transfer functions 1.1 Introduction [1] . . . . . . . . . . . . . . . . . . . 1.2 Nyquist diagram . . . . . . . . . . . . . . . . . . 1.2.1 Nyquist diagram used by electricians . . . 1.2.2 Nyquist diagram used by electrochemists 1.3 Bode diagram . . . . . . . . . . . . . . . . . . . . 1.3.1 Bode diagram used by electricians . . . . 1.3.2 Bode diagram used by electrochemists . . 1.4 Black diagram . . . . . . . . . . . . . . . . . . . 1.4.1 Black diagram used by electrician . . . . . 1.4.2 Black diagram used by electrochemists . . 1.5 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 5 6 6 6 6 6 6 6 6 6 7 9 9 9 9 11 11 11 11 11 15 15 15 15 16 16 16 20 20 20 20 20 20

2 First-order transfer functions 2.1 First-order transfer function [2, 7] . . . . . . . . . . . 2.1.1 First-order transfer function . . . . . . . . . . 2.1.2 Dimensionless rst-order transfer function . . 2.2 Generalized rst-order transfer functions . . . . . . . 2.2.1 High-pass rst-order transfer function . . . . 2.2.2 Dimensionless high-pass rst-order transfer function . . . . . . . . . . . . . . . . . . . . . 2.2.3 Generalized rst-order transfer function . . . 2.2.4 Dimensionless generalized rst-order transfer function . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3 Second-order transfer functions 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1.1 Canonical form . . . . . . . . . . . . . . . . . . . . 3.1.2 Reduced form . . . . . . . . . . . . . . . . . . . . . 3.1.3 Second-order transfer function with real poles . . . 3.1.4 Second-order transfer function with complex poles 3.1.5 Second-order transfer function with multiple poles 3.2 Generalized second-order transfer functions . . . . . . . . 3.2.1 Generalized second-order transfer functions . . . . 3.2.2 Electrochemical examples . . . . . . . . . . . . . . 3.2.3 Canonical form . . . . . . . . . . . . . . . . . . . . 3.2.4 Reduced form . . . . . . . . . . . . . . . . . . . . . 3.2.5 Complex poles < 1 . . . . . . . . . . . . . . . . . 3

4 3.2.6 3.2.7

CONTENTS Multiple poles = 1 . . . . . . . . . . . . . . . . . . . . . Real poles > 1 . . . . . . . . . . . . . . . . . . . . . . . 23 25

4 Appendix: 3D-plot of transfer functions 27 4.1 3D-plot of modulus [3] . . . . . . . . . . . . . . . . . . . . . . . . 27 4.1.1 First order transfer function . . . . . . . . . . . . . . . . . 27 4.1.2 Second order transfer function . . . . . . . . . . . . . . . 27 Bibliography 29

Chapter 1

Graphs of transfer functions

1.1 Introduction [1]
Input System Output

Figure 1.1: Sketch of a scalar system. The transfer function, H, of a invariant scalar linear system is given by: H(s) = L[Output] L[Input]

L denotes the Laplace transform, s is the Laplace variable with s = +i . For current input and potential output, H is an impedance. A transfer function is a complex fonction H(s) of two real variables and . It is not possible to plot graph of H(s) in a plane, only 3D-plots are possible [3] (cf. Chap. 4). For s = i , i.e. = 0, corresponding to frequencial analysis, a transfer function is a complex fonction H = H(i ) (or H()) of a real variable . It is possible to plot graph of H = H() in a plane and dierent types of graph can be used. The order of rational fraction transfer function is the degree in s (or i ) of the transfer function denominator. The relativer order of rational fraction transfer function is the difference between the order of the denominator and the order of the numerator. A proper system is a system where the degree of the denominator is larger or equal to the degree of the numerator. A strictly proper system is a system where the degree of the denominator is larger than the degree of the numerator. 5

CHAPTER 1. GRAPHS OF TRANSFER FUNCTIONS Poles of transfer function are the roots of the denominator of the transfer function H(s). Dominant poles: poles closest to the imaginary axis Zeros of transfer function are the roots of the numerator of the transfer function H(s).

1.2
1.2.1

Nyquist diagram
Nyquist diagram used by electricians

Orthonormal parametric plot x = Re H = f (), y = Im H = g() (1.1)

1.2.2

Nyquist diagram used by electrochemists

Orthonormal parametric plot x = Re H = f (), y = Im H = g() (1.2)

1.3
1.3.1

Bode diagram
Bode diagram used by electricians

Modulus diagram: 20 log |H| vs. log . |H| is the modulus (or magnitude or amplitude) of H with |H| = (Re H)2 + (Im H)2 . Phase diagram: H vs. log . H is the phase of H with H = arctan Im H Re H

1.3.2

Bode diagram used by electrochemists

log |H| vs. log , H vs. log (1.3)

1.4
1.4.1

Black diagram
Black diagram used by electrician
x = H = f (), y = 20 log |H| = g() (1.4)

Parametric plot

1.4.2

Black diagram used by electrochemists

x = H = f (), y = log |H| = g() (1.5)

Parametric plot

1.5. MISCELLANEOUS

1.5

Miscellaneous

Re H vs. log , Im H vs. log log Re H vs. log , log Im H vs. log [10, 9] log Im H vs. log Re H [6], log |Im H| vs. log |Re H|

CHAPTER 1. GRAPHS OF TRANSFER FUNCTIONS

Chapter 2

First-order and generalized rst-order transfer functions

2.1
2.1.1

First-order transfer function [2, 7]

First-order transfer function
H(s) =

K K , H() = 1 + s 1 + i K: static gain, : time constant.

2.1.2

Dimensionless rst-order transfer function

H (S) = H(s) 1 = , S = s = + i u, = , u = K 1+S

One real pole: Sp = 1 (Fig. 2.1). H (u) = 1 H() = , u= K 1 + iu (2.1)

u: reduced (or dimensionless or nondimensional) angular (or radial) frequency Re H (u) = 1 u , Im H (u) = , lim Re H (u) = 1 1 + u2 1 + u2 u0

Characteristic frequency: uc = 1 (Fig. 2.1).

10

CHAPTER 2. FIRST-ORDER TRANSFER FUNCTIONS

H u

1 1 iu

a 0.5 Im H

uc

log H

1 1

0 0 0.5 Re H 0 log Im H b uc 1 H degrees 1

log uc log u

45

2 log Re H

90 2 log uc log u 0 f uc log H 1 1 0 2

1 Im H Re H ,

0 2 0 log u 2

2 90 45 H degrees 0

Figure 2.1: Pole-zero map, Nyquist (a), log Nyquist (b) Re H vs. log u (c, thick line), Im H vs. log u (c, thin line), Bode (modulus (c) and phase (d)) and Black diagrams of the rst order transfer function H (u) = 1/(1 + i u). Arrow always indicates increasing angular frequencies.

2.2. GENERALIZED FIRST-ORDER TRANSFER FUNCTIONS

11

2.2
2.2.1

Generalized rst-order transfer functions

High-pass rst-order transfer function
H(s) = K N i K N s , H() = 1 + D s 1 + D i

2.2.2

Dimensionless high-pass rst-order transfer function

H(s) S N = , S = D s = + i u, = D , u = D w , r = K r 1+S D

H (S) =

One real pole: Sp = 1, one zero at the origin: Sz = 0 (Fig. 2.2). H (u) = Re H (u) = iu H() = , u = D r 1 + iu u u2 , Im H (u) = 2 1+u 1 + u2

lim Re H (u) = 1

Characteristic frequency: uc = 1 (Fig. 2.2).

2.2.3

Generalized rst-order transfer function

H(s) = K (1 + N i ) K (1 + N s) , H() = 1 + D s 1 + D i

2.2.4
H (S) =

Dimensionless generalized rst-order transfer function

H(S) 1 + r S N , S = D s = + i u, = D , u = D = , r = K 1+S D

One real pole: Sp = 1 = uc1 , one real zero: Sz = 1/r = uc2 . H (u) = Re H (u) =
u0

1 + i r u H(u) = K 1 + iu

1 + r u2 (1 + r ) u , Im H (u) = 2 1+u 1 + u2
u

lim Re H (u) = 1, lim Re H (u) = r

Characteristic frequency: uc1 = 1, uc2 = 1/r (uc1 = uc2 ). r < 1 Capacitive behaviour (Fig. 2.3). r > 1 Inductive behaviour (Fig. 2.4).

12

CHAPTER 2. FIRST-ORDER TRANSFER FUNCTIONS

H u

iu 1 iu

a log H

Im H

uc 0.5

2 0 0.5 Re H 0 log Im H b uc 1 H degrees 90 1 2 log uc log u e 0 2

45

0 3 2 log Re H 1 0 2 log uc log u 0 f uc log H 1 1 0 2

1 Im H Re H , 0

2 2 log uc log u 0 2 0 45 H degrees 90

Figure 2.2: Pole-zero map, Nyquist (a), log Nyquist (b) Re H vs. log u (c, thick
line), Im H vs. log u (c, thin line), Bode (modulus (c) and phase (d)) and Black diagrams of the high-pass rst-order transfer function. Arrow always indicates increasing angular frequencies.

2.2. GENERALIZED FIRST-ORDER TRANSFER FUNCTIONS

13

H u

1 1

r i u iu

uc2

0.5 a Im H

log H 0.5 0 0 r Re H 0 b 1 2 0 log u 2 0.5 H degrees 20

log Im H

1 1 log Re H 1 Im H 0

40 2 0 log u 0 f

e 2

c log H 2 0 log u 2

Re H ,

0.5

0.5

0 40 20 H degrees 0

Figure 2.3: Pole-zero map, Nyquist (a), log Nyquist (b) Re H vs. log u (c, thick
line), Im H vs. log u (c, thin line), Bode (modulus (c) and phase (d)) and Black diagrams of the generalized rst order transfer function. r = 0.2 (r < 1), dot: uc1 = 1, circle: uc2 = 1/r .

14

CHAPTER 2. FIRST-ORDER TRANSFER FUNCTIONS

H u

1 1

r i u iu

uc2

0.4 log H

Im H 1 a 0 1 Re H 0 b r

0 2 0 log u e H degrees 20 10 0 2 0 log u 2 2

log

Im H 0.5 0 0.5 log Re H 3 Im H 2 1 0 c

f log H

Re H ,

0.2

0 2 0 log u 2 0 10 20 H degrees

Figure 2.4: Pole-zero map, Nyquist (a), log Nyquist (b) Re H vs. log u (c, thick line), Im H vs. log u (c, thin line), Bode (modulus (c) and phase (d)) and Black diagrams of the generalized rst order transfer function. r = 3 (r > 1), dot: uc1 = 1, circle: uc2 = 1/r .

Chapter 3

Second-order and generalized second-order transfer functions

3.1 Introduction
H(s) = K 1 + a 1 s + a 2 s2

3.1.1

Canonical form
H(s) = 1+2 K s + n s n
2

poles: sp1 = n > 1, two real poles = 1 multiple pole < 1 complex poles
2 ( 2 1) n , sp2 = n + 2 ( 2 1) n

3.1.2
H (S) = poles:

Reduced form
H(s) s + i 1 , S= = = +i u, = ,u= = 2 K 1+2 S +S n n n n

Sp1 =

2 1, Sp2 = + 15

2 1

16

CHAPTER 3. SECOND-ORDER TRANSFER FUNCTIONS

3.1.3

Second-order transfer function with real poles

H(s) = K K , H() = (1 + 1 s) (1 + 2 s) (1 + 1 i ) (1 + 2 i )

H (S) =

1 2 H(s) = , S = 1 s = +i u, = 1 , u = 1 , r = K (1 + S) (1 + r S) 1

Two real poles: Sp1 = 1 = uc1 , Sp2 = 1/r = uc2 (Fig. 3.1). H (u) = Re H (u) = 1 (1 + i u) (1 + r i u)

1 u2 r u (1 + r ) , Im H (u) = (1 + u2 ) (1 + u2 r 2 ) (1 + u2 ) (1 + u2 r 2 )

3.1.4

Second-order transfer function with complex poles

H (S) = 1 , <1 1 + 2 S + S2

Two complex poles (Fig. 3.2) : Sp1 = 2 1 = i H (u) = 1 2 , Sp2 = + 2 1 = + i 1 2

1 , <1 1 + 2 i u + (i u)2

Re H (u) =

u4

2u 1 u2 , Im H (u) = 4 + (4 2 2) u2 + 1 u + (4 2 2) u2 + 1

3.1.5

Second-order transfer function with multiple poles

H (S) = 1 1 , = 1 H (S) = 1 + 2 S + S2 (1 + S)2

One multiple pole: Sp = 1 uc = 1 (Fig. 3.3). H (u) = 1 u2 1 (1 + i u)2 Im H (u) = 2u (u2 + 1)

2

Re H (u) =

(u2

+ 1)

2,

dIm (u) 3 1 = 0 = , H (u) = (1 i 3) du 8 3 1 dRe (u) = 0 = 3, H (u) = (1 + i 3) du 8

3.1. INTRODUCTION

17

H u

1 1 iu 1 r i u

uc2

a 0.5 log H

Im H

0 0 Re H 0 f H degrees 1

4 2 0 log u 0 2

log Im H

90

2 3 2 log Re H 1 Im H c 1 0

180 2 0 log u 0 2

log H 0 2 0 log u 2

Re H ,

4 180 90 H degrees 0

Figure 3.1: Pole-zero map, Nyquist (a), log Nyquist (b) Re H vs. log u (c, thick
line), Im H vs. log u (c, thin line), Bode (modulus (c) and phase (d)) and Black diagrams of the reduced second order transfer function with real poles H = 1/((1 + i u) (1 + r i u)). r = 2 (r > 1), dot: uc1 = 1, circle: uc2 = 1/r .

18

CHAPTER 3. SECOND-ORDER TRANSFER FUNCTIONS

H u 1

2 iu

iu

0 1 2 0

1 Im H

uc 1

log H
0

4
0 Re H 1

0 log u

b 0 H degrees log Im H 0 e

90

180 2 2 1 log Re H 0 2 0 log u 2

1 Im H

0 1 log H 2 3

uc 1

Re H ,

0 180 90 H degrees 0

0 log u

Figure 3.2: Pole-zero map, Nyquist (a), log Nyquist (b) Re H vs. log u (c, thick
line), Im H vs. log u (c, thin line), Bode (modulus (c) and phase (d)) and Black diagrams of the reduced second order transfer function with complex poles H (u) = 1/(1 + 2 i u + (i u)2 ), = 0.5.

3.1. INTRODUCTION

19

H u 1

1 iu
2

0
a Im H uc 3 1 1 3

log H
1

0 Re H

4 2 0 log u 2

b 0 H degrees log Im H 0 e

90

180 2 2 1 log Re H 0 2 0 log u 2

1 Im H

0 1 log H 2

f uc 1

Re H , 0 2 0 log u 2

3 180

90 H degrees

Figure 3.3: Pole-zero map, Nyquist (a), log Nyquist (b) Re H vs. log u (c, thick line),
Im H vs. log u (c, thin line), Bode (modulus (c) and phase (d)) and Black diagrams of the reduced second order transfer function with multiple poles H (u) = 1/(1 + i u)2 .

20

CHAPTER 3. SECOND-ORDER TRANSFER FUNCTIONS

3.2
3.2.1

Generalized second-order transfer functions

Generalized second-order transfer functions
H(s) = K (1 + b1 s) 1 + a1 s + a2 s2

3.2.2

Electrochemical examples
r1 A+ + s + e A,s

Volmer-Heyrovsk reaction with chemical desorption [8, 4, 5] y

K

r2 A+ + A,s + e A2 ,s d3 A2 ,s A2 + s

Schuhmann dissolution-passivation reaction # 1 [11]

o1 M,s X,s + 2 e

Kr1

X,s Q,s + 2 e
Kr2 K
o3 X,s + A X,s + B + 2 e

Ko2

3.2.3

Canonical form
H(s) = K (1 + b1 s) 1+2 s + n s n
2

poles: > 1, two real poles, = 1 multiple pole, < 1 complex poles (cf. 3.1.1). sp1 = n
2 ( 2 1) n , sp2 = n + 2 ( 2 1) n

3.2.4
H (S) =

Reduced form
H(s) s + i 1+T S , S= = = +i u, = ,u= = 2 K 1+2S +S n n n n 2 1, Sp2 = + 2 1, zero: Sz = 1/T .

poles: Sp1 = Re H (u) =

u T u2 + T 2 (2T 1)u2 + 1 , Im H (u) = 4 u4 + (4 2 2) u2 + 1 u + (4 2 2) u2 + 1 Im H (u) > 0 (inductif behaviour) for 0 < u < T 2 / T if T > 2 .

3.2.5

Complex poles < 1

T > 1: Fig. 3.4, T = 1: Fig. 3.5, T < 1: Figs. 3.6 and 3.7.

3.2. GENERALIZED SECOND-ORDER TRANSFER FUNCTIONS

1 1 0 1 2 1 Re S 0 2 1 0 log u 1 2

21

log H H

Im S

Im H

1 0

90 2 0 1 Re H 1 0 log u 1 2

Figure 3.4:

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with complex poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 0.5, T = 10.
1 0 log H 1 2 3 1 Re S 0 2 1 0 log u 1 2

Im S 1

Im H

H 90 0 0 Re H 1 2 1 0 log u 1 2

Figure 3.5:

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with complex poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 0.5, T = 1.

22
1

CHAPTER 3. SECOND-ORDER TRANSFER FUNCTIONS

0 1

log H

Im S

2 3

1 Re S 1

0 log u

Im H

H 90 0 0 Re H 1 2 1 0 log u 1 2 1 0 1 0 log H Im S 2 3 4 1 Re S 0 2 1 0 log u 1 2 1 0 H 90

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with complex poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 0.5, T = 0.5.

Figure 3.6:

Im H

0 0 Re H 1

0 log u

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with complex poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 0.5, T = 0.1. Zero not shown in the pole-zero map.

Figure 3.7:

3.2. GENERALIZED SECOND-ORDER TRANSFER FUNCTIONS

23

3.2.6

Multiple poles = 1

T > 1: Fig. 3.8, T = 1: Fig. 3.9, T < 1: Fig. 3.10.

1 0 0 log H Im S 1 2 1 Re S 0 2 1 0 log u 1 2

Im H

1 0 H

90 2 0 1 Re H 1 0 log u 1 2

Figure 3.8:

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with multiple poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 1, T = 10.

24
1

CHAPTER 3. SECOND-ORDER TRANSFER FUNCTIONS

0 1 2 3 1 Re S 0 2 1 0 log u 1 2

log H H 1 Re H

Im S

Im H 0 0

90 2 1 0 log u 1 2

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with multiple poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 1, T = 1.
1

Figure 3.9:

0 1

log H

Im S

2 3 4 2 1 0 log u 1 2

1 Re S

Im H

H 90 0 0 Re H 1 2 1 0 log u 1 2

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with multiple poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 1, T = 1. Zero not shown in the pole-zero map

Figure 3.10:

3.2. GENERALIZED SECOND-ORDER TRANSFER FUNCTIONS

25

3.2.7

Real poles > 1

: Fig. 3.11,

: Fig. 3.12,

: Fig. 3.13.
1 0 log H Im S

2 1 Re S 0 2 1 0 log u 1 2

0 Im H

0 90 2 0 Re H 1 1 0 log u 1 2

Figure 3.11:

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with real poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 3, T = 10.

26
1

CHAPTER 3. SECOND-ORDER TRANSFER FUNCTIONS

0

log H

Im S

2 2 1 0 log u 1 2

1 Re S

Im H

0 0 Re H 1 90 2 1 0 log u 1 2

Figure 3.12:

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with real poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 3, T = 3.16. One pole not shown in the polezero map.
1 0 1 0 log H Im S 2 3 4 2 1 0 log u 1 2

1 Re S

H 0 H 0 0 Re H 1 2 1 0 log u 1 2 90

Figure 3.13:

Pole-zero map, Nyquist, Bode (modulus and phase) of the reduced generalized second-order transfer function with real poles H (u) = (1 + T i u)/(1 + 2 i u + (i u)2 ). = 3, T = 102 . Zero and one pole not shown in the pole-zero map.

Im H

Chapter 4

Appendix: 3D-plot of transfer functions

4.1
4.1.1

3D-plot of modulus [3]

First order transfer function
H (S) = 1 , S = + iu 1+S

10 2 H

0 2

u 1 0 0

Figure 4.1: 3D-plot of the modulus of rst order transfer function.

4.1.2

Second order transfer function

1 , S = + i u, < 1 1 + 2 S + S2 27

Complex poles H (S) =

28

CHAPTER 4. APPENDIX: 3D-PLOT OF TRANSFER FUNCTIONS

2 H 1 0 0 u 1 0 2 1 2 2

Figure 4.2: 3D-plot of the modulus of second order transfer function. Complex poles,
= 0.5

Real poles H (S) = 1 , S = + iu (1 + S) (1 + r S)

2 H

0 2

u 1 0 0

Figure 4.3: 3D-plot of the modulus of second order transfer function. Real poles,
r = 5

Bibliography
[1] Control systems/system metrics. http://en.wikibooks.org/wiki/Control Systems. [2] de Larminat, P., and Tomas, Y. Automatique des syst`mes linaire. e e I. S ignaux et syst`mes. Flammarion, Paris, 1975. e [3] Diard, J.-P., LeGorrec, B., and Montella, C. Il ny a pas que j . In Proceeding of the 7th Forum sur les Impdances e Electrochimiques (Montrouge, 1993), C. Gabrielli, Ed., pp. 133138. http://www.Electrochimie.org. [4] Diard, J.-P., LeGorrec, B., Montella, C., and MonteroOcampo, C. Second order electrochemical impedances and electrical resonance phenomenon. Electrochim. Acta 37 (1992), 177179. [5] Diard, J.-P., LeGorrec, B., Montella, C., and MonteroOcampo, C. Calculation, simulation and interpretation of electrochemical impedance diagrams. part IV. Second-order electrochemical impedances. J. Electroanal. Chem. 352 (1993), 115. [6] Fournier, J., Wrona, P. K., Lasia, A., Lacasse, R., Lalancette, J.-M., Menard, H., and Brossard, L. J. Electrochem. Soc. 139 (1992), 2372. [7] Gille, J.-C., Decaulne, P., and Plegrin, M. Dynamique de la e commande linaire. Dunod, Paris, 1991. e [8] Montero-Ocampo, C. Impdances lectrochimiques du second ordre. Exe e emple du mcanisme de Volmer-Heyrovsk avec dsorption chimique. PhD e y e thesis, Institut National Polytechnique de Grenoble, Grenoble, 1988. [9] Orazem, M. E., Pb`re, N., and Tribollet, B. J. Electrochem. Soc e e 153 (2006), B129. [10] Rodiguez-Presa, M. J., Tucceri, R. I., Florit, M. I., and Posadas, D. Constant phase element behavior int the poly(o-toluidine) impedance response. J. Electroanal. Chem. 502 (2001), 8290. e e e a e e [11] Schuhmann, D. tude phnomnologique ` laide de schmas ractionnels des impdances faradiques contenant des rsistances ngatives et des induce e e tances. J. Electroanal. Chem. 17 (1968), 4559.

29