Handbook of Electrochemical Impedance Spectroscopy

0.5 - Im Z* 0 0 0.5 Re Z* 1

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

May 18, 2012

Contents
1 Mass transfer by diusion, Nernst boundary condition 1.1 General diusion equations . . . . . . . . . . . . . . . . . . . . . 1.2 Semi-innite diusion . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 Semi-innite linear diusion . . . . . . . . . . . . . . . . . 1.2.2 Semi-innite radial cylindrical diusion (outside) . . . . . 1.2.3 Semi-innite spherical diusion . . . . . . . . . . . . . . . 1.3 Bounded diusion condition (linear diusion) . . . . . . . . . . . 1.3.1 Randles circuit . . . . . . . . . . . . . . . . . . . . . . . . 1.3.2 Corrosion equivalent circuit . . . . . . . . . . . . . . . . . 1.4 Radial cylindrical diusion . . . . . . . . . . . . . . . . . . . . . . 1.4.1 Finite-length diusion outside a cylinder . . . . . . . . . . 1.4.2 Semi-innite outside a cylinder . . . . . . . . . . . . . . . 1.5 Spherical diusion . . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.1 Finite-length difusion outside a sphere, reduced impedance #1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.2 Finite outside sphere, reduced impedance # 2 . . . . . . . 1.5.3 Innite outside sphere . . . . . . . . . . . . . . . . . . . . 2 Mass transfer by diusion, restricted diusion 2.1 General diusion equations . . . . . . . . . . . . . . 2.1.1 Internal cylinder and sphere with null radius 2.2 Linear diusion . . . . . . . . . . . . . . . . . . . . . 2.2.1 Modied restricted diusion impedance . . . 2.2.2 Anomalous diusion impedance . . . . . . . . 2.3 Cylindrical diusion . . . . . . . . . . . . . . . . . . 2.4 Spherical diusion . . . . . . . . . . . . . . . . . . . 2.4.1 Randles circuit for restricted linear diusion . 3 Gerischer and diusion-reaction impedance 3.1 Gerischer and modied Gerischer impedance 3.1.1 Gerischer impedance . . . . . . . . . . 3.1.2 Modied Gerischer impedance #1 . . 3.1.3 Modied Gerischer impedance #2 . . 3.2 Diusion-reaction impedance . . . . . . . . . 3.2.1 Reduced impedance #1 . . . . . . . . 3.2.2 Reduced impedance #2 . . . . . . . . 3.3 Appendix . . . . . . . . . . . . . . . . . . . . 5 5 6 6 7 8 8 10 10 12 12 12 13 13 13 13 15 15 15 16 17 17 18 18 19 21 21 21 22 23 24 24 24 26

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CONTENTS

Chapter 1

Mass transfer by diusion, Nernst boundary condition

1.1
From: c(x, t) = D x1d t x

General diusion equations

( ) c(x, t) xd1 x

where denotes a smal deviation (or excursion) from the initial steady-state value, d = 1 corresponds to a planar electrode, d = 2 to a cylindrical electrode (radial diusion) and d = 3 to a spherical electrode [5, 25] (Fig. 1.1), it is obtained, using the Nernstian boundary condition c(r ) = 0: Id/21 ( i u ) Kd/21 ( i u) Id/21 ( i u) Kd/21 ( i u ) J(r0 , i u) Z (u) = c(r0 , i u) i u (Id/2 ( i u) Kd/21 ( i u ) + Id/21 ( i u ) Kd/2 ( i u))

where u is a reduced frequency and = r /r0 . In (z) gives the modied Bessel function of the rst kind and order n and Kn (z) gives the modied Bessel function of the second kind and order n [37]. In (z) and Kn (z) satisfy the dierential equation: ( ) y n2 + z 2 + z y + z 2 y = 0

r0 r

r0

r0

Figure 1.1: Planar difusion (left), outside [15] (or convex [22]) diusion ( = r /r0 > 1, middle), and central (or concave) diusion ( < 1, right).

6CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

1.2
1.2.1

Semi-innite diusion
Semi-innite linear diusion

d = 1, c() = 0 Impedance [34, 4]

Figure 1.2: Warburg element [36].

(1 i) 2 = , Re ZW () = , Im ZW () = i 1 F = 2 , f= , X : bulk concentration, unit: cm2 s1/2 RT n F f X 2 DX ZW () = Reduced impedance 1 1 1 ZW (u) = ZW () = , u = , Re ZW (u) = , Im ZW (u) = 2 2 2u 2u iu

1 u Im ZW 1

4 0 0 Re ZW 1

Figure 1.3: Nyquist diagram of the reduced Warburg impedance.

Randles circuit The equivalent circuit in Fig. 1.4 was initially proposed by Randles for a redox reaction O + ne R [28]. = O + R

1.2. SEMI-INFINITE DIFFUSION

Cdl

Rct

Figure 1.4: Randles circuit for semi-innite linear diusion.

Impedance Z() = 1 1 i Cdl + (1 i) Rct + = i ((1 i) +

Rct )
3

i + (1 i) Cdl + 2 Cdl Rct

+ Rct ( ) Re Z() = 3 1 + 2 Cdl + 2 2 Cdl 2 + 2 2 Cdl 2 Rct + 2 Cdl 2 Rct 2 3 2 2 Cdl 2 Cdl Rct 2 Cdl Rct 2 ) Im Z() = ( 3 1 + 2 Cdl + 2 2 Cdl 2 + 2 2 Cdl 2 Rct + 2 Cdl 2 Rct 2 Reduced impedance The frequency response of the Randles circuit can be described in terms of two time constants for faradaic (f ) and diusional (d ) processes [35] (Fig. 1.5). (1 + i) T (i + u) Z(u) = Rct T 2 u + (1 + i) (1 + T + i u) u ( ) 2 u = d , d = Rct / 2 2 , T = d /f , f = Rct Cdl ( ( ) ) 3 T 2 2 (1 + u) + 2 u 2 ) Re Z (u) = ( 2 2 2 T u (1 T + u) + 2 u T 2 + (1 + T ) u + u3 ( )) ( T 2 T (1 u) 2 u 1 T + u2 ) Im Z (u) = ( 2 2 2 T u (1 T + u) + 2 u T 2 + (1 + T ) u + u3 Z (u) =
u0

lim Re Z (u) = 1

1 1 1 + , lim Im Z (u) = T 2 u u0 2u

1.2.2

Semi-innite radial cylindrical diusion (outside)

K0 ( i u) Z (u) = i u K1 ( i u) lim Im Z (u) = , Re Z (uc ) = uc = 0.542 u0 4 4

d = 2, c() = 0

(Fig. 1.6)

8CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

a 2 Im Z Im Z 2

1 Re Z

1 1T Re Z

Figure 1.5: a: Nyquist diagram of the reduced impedance for the Randles circuit
(Fig. 1.4). Semi-innite linear diusion. T = 1, 2, 5, 10, 16.4822, 102 , 104 . Line thickness increases with T . One apex for T > 16.4822. The arrows always indicate the increasing frequency direction. b: Extrapolation of the low frequency limit plotted for T = 5.

1 4 Im Z uc 0.542 0 0 4 2 Re Z 4

Figure 1.6: Reduced impedance for semi-innite radial diusion outside a cicrcular
cylinder. Dot: reduced characteristic angular frequency: uc = 0.542.

1.2.3

Semi-innite spherical diusion

d = 3, c() = 0 1 2 , u = r0 /D Z (u) = 1 + iu 2 + 2u u ) , Im Z (u) = ( ) Re Z (u) = ( 2 1 + 2u + u 2 1 + 2u + u (Fig. 1.7)

1.3

Bounded diusion condition (linear diusion)

c(r ) = 0 Originally derived by Llopis and Colon [20], and subsequently re-derived by Sluyters [31] and Yzermans [39], Drossbach and Schultz [13], and Schuhmann [30] [4].

1.3. BOUNDED DIFFUSION CONDITION (LINEAR DIFFUSION)

Im Z

uc 1 0.2 0 0 0.5 Re Z 1

Figure 1.7: Reduced impedance for spherical (outside) diusion. Dot: reduced char acteristic angular frequency: uc = 1, Re Z (uc ) = 1/2, Im Z (uc ) = (1 2)/2.

IUPAC terminology: bounded diusion [32] Finite-length diusion with transmissive boundary condition [17, 21] tanh i u , u = d , d = 2 /D, = 2 u = iu lim ZW (u) = 1, lim i u ZW (u) = 1
u

ZW (u)

u0 Re ZW () =

sin() + sinh() sin() sinh() , Im ZW () = (cos() + cosh()) (cos() + cosh())

Figure 1.8: Bounded diusion impedance.

0.5 Im ZW

uc 2.541

4 0 0 0.5 Re ZW 1

Figure 1.9: Nyquist diagram of the reduced bounded diusion impedance.

10CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

Cdl

Rct

Figure 1.10: Randles circuit for bounded diusion.

1.3.1

Randles circuit
tanh i u Zf (u) = Rct + Rd , u = d , d = 2 /D iu sin() + sinh() Re Zf () = Rct + Rd , = 2u (cos() + cosh()) sin() sinh() Im Zf () = Rd (cos() + cosh()) tanh i u iu ) tanh i u Rct + Rd iu

Impedance

Z(u) =

Zf (u) = 1 + i (u/d ) Cdl Zf (u)

Rct + Rd ( 1 + i (u/d ) Cdl

Reduced impedance (Fig. 1.11) tanh i u 1+ iu

Z (u) =

Z(u) =( ) )( Rct + Rd T tanh i u 1 1 + iuT + iu 1+ iu = Rct /Rd , T = f /d , f = Rct Cdl

1.3.2

Corrosion equivalent circuit

Corrosion of a metal M with limitation by mass transport of oxidant (Fig. 1.12) on a rotating disk electrode (RDE) [26]. tanh i u Rct Rd iu , u = d , d = 2 /D (1.1) Z(u) = tanh i u Rct + Rd iu

1.3. BOUNDED DIFFUSION CONDITION (LINEAR DIFFUSION)

11

log 2 4 log T 0
Figure 1.11: Impedance diagram array for the Randles circuit with bounded diusion
(Fig. 1.10).

Rct

Figure 1.12: Equivalent circuit for corrosion of a metal M with limitation by mass
transport of oxidant. Rct : charge transfer of the reaction of metal oxidation.

tanh i u Z(u) Rd iu Z (u) = (1 + ) = (1 + ) , = Rd Rct tanh i u 1+ iu Two limiting cases (Fig. 1.13): 1: Z (u) 1: Z (u) , uc2 = 2 , quarter of circle, (Fig. 1.7) + iu

(1.2)

tanh i u , uc1 = 2.541, quarter of lemniscate, (Fig. 1.8) (1.3) iu

(1.4)

12CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

0.5 Im Z
2

10

2.541 102

0.5 Re Z

Figure 1.13: Nyquist diagram of the corrosion equivalent circuit. Large black dot :
uc1 = 2.541, small red dot : uc2 = 2 .

1.4

Radial cylindrical diusion

d = 2 [15] (Fig. 1.1)

1.4.1

Finite-length diusion outside a cylinder

Z (u) =

I0 ( i u ) K0 ( i u) I0 ( i u) K0 ( i u ) ( ) Log() i u I1 ( i u) K0 ( i u ) + I0 ( i u ) K1 ( i u)
2 u = r0 /D, = r /r0

Fig. 1.14 recties erroneous Figs. 7 and 8 in [23].

0.5 - Im Z* 0 0 0.5 Re Z* 1

Figure 1.14: Central ( < 1) and outside ( > 1) cylindrical diusion impedance.

= r /r0 = 102 , 101 , 0.4, 1.01, 2, 5, 20, 100. The line thickness increases with . Dots: reduced characteristic angular frequency (apex of the impedance arc): uc = 0.514484, 1.22194, 4.74992, 25516., 3.40142, 0.298271, 0.0186746, 0.000800438.

1.4.2

Semi-innite outside a cylinder

lim Z (u) =

K0 ( i u) i u K1 ( i u)

(Fig. 1.6)

1.5. SPHERICAL DIFFUSION

13

1.5

Spherical diusion

d = 3 [15] (Fig. 1.1)

1.5.1

Finite-length difusion outside a sphere, reduced impedance #1

1

(Fig. 1.15) Z (u) = (

2 ) , u = r0 /D, = r /r0 i u coth( i u (1 + ))

(1 1/) 1 +

0.5 - Im Z* log uc 0 0 0.5 Re Z* 1

2 1 0 -1 0 1 5 r 10

Figure 1.15: Central ( < 1) and outside ( > 1) spherical diusion impedance. =
r /r0 = 0.1, 0.4, 0.91, 1.1, 2, 5, 50. Line thickness increases with . Dots: reduced char2 acteristic angular frequency: uc = r0 /D = 0.3632, 3.095, 289, 275.8, 4.547, 0.6927, 1. Change of log uc with .

1.5.2

Finite outside sphere, reduced impedance # 2

1+ , u = (r r0 )2 /D, = (r r0 )/r0 i u coth( i u)

(Fig. 1.16) Z (u) =

1.5.3

Innite outside sphere

lim Z (u) = 1
2 , u = r0 /D

(Fig. 1.7)

u 2 + 2u ) , Im Z (u) = ( ) Re Z (u) = ( 2 1 + 2u 2 1 + 2u + u

1+

iu

14CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

0.5 - Im Z* log uc

2 1 0 -1 -1 0 d log 2.54

0 0 0.5 Re Z* 1

10

Figure 1.16: Central ( < 0) and outside ( > 0) spherical diusion impedance.
= (r r0 )/r0 = 0.99, 0.8, 0.5, 0.1, 0.1, 1, 3, 100. Line thickness increases with . Dots: reduced characteristic angular frequency: uc = (r r0 )2 /D = 0.0299, 0.577, 1.37, 2.32, 2.76, 4.55, 8.33, 104 , uc increases with . Change of log uc with .

Chapter 2

Mass transfer by diusion, restricted diusion

2.1
From:

General diusion equations

( ) c(x, t) 1d d1 c(x, t) = Dx x t x x where denotes a smal deviation (or excursion) from the initial steady-state value, d = 1 corresponds to a planar electrode, d = 2 to a cylindrical electrode (radial diusion) and d = 3 to a spherical electrode [5, 25] (Fig. 1.1), it is obtained, using the condition J(r ) = 0: Id/21 ( i u) Kd/2 ( i u ) + Id/2 ( i u ) Kd/21 ( i u) J(r0 , i u) Z (u) = c(r0 , i u) i u (Id/2 ( i u ) Kd/2 ( i u) Id/2 ( i u) Kd/2 ( i u )) Terminology [24]: bounded system [16], nite-space diusion [1, 2], nite length diusion [18], restricted diusion [10, 9, 12], reective boundary condition [27], impermeable boundary [38], impermeable barrier condition [15], impermeable surface [11].

2.1.1
r0 = 0,

Internal cylinder and sphere with null radius

,d

Figure 2.1: Restricted diusion impedance. d = 1: thin planar layer, d = 2: cylinder, d = 3: sphere. Id/21 ( i u) Z (u) = i u Id/2 ( i u)

15

16CHAPTER 2. MASS TRANSFER BY DIFFUSION, RESTRICTED DIFFUSION Low frequency limit Fig. 2.2. u 0 Z (u) 1 id d+2 u

C ,d R

1/(d + 2), C = 1/d.

Figure 2.2: Low frequency equivalent circuit for restricted diusion impedance. R =

High frequency limit Fig. 2.3. 1 u Z (u) , lim i u Z (u) = 1 u iu

,d
Figure 2.3: High frequency equivalent circuit for restricted diusion impedance.

2.2
d=1

Linear diusion
Id/21 ( i u) I1/2 ( i u) coth i u Z (u) = = = i u Id/2 ( i u) i u I1/2 ( i u) iu

u0

lim Z (u) =

i 1 , lim i u Z (u) = 1 u 3 u u = d , d = 2 /D, = 2 u

Re Z () =

sin() + sinh() sin() sinh() ; Im Z () = (cos() cosh()) (cos() cosh())

Reduced characteristic angular frequency: uc1 3 (d(d+2)) [5], 5.12 [3], 4 [8], 3.88 [7].

2.2. LINEAR DIFFUSION

17

d 1 1 1

d 2 1

d 3

Im Z

Im Z

uc 3.88

uc 11.7

Im Z

13 14 15

0 0 Re Z 13

0 0 14 Re Z

0 0 15 Re Z

Figure 2.4: Nyquist diagram of the reduced impedance for the restricted diusion
impedance plotted for d = 1, 2, 3. Dots: reduced characteristic angular frequency: uc1 = 3.88, uc2 = 11.7, uc3 = 22.3.

2.2.1

Modied restricted diusion impedance

i u replaced by (i u) 2 (: dispersion parameter) [8, 7, 29] Z (u) =

, u = d , d = 2 /D (i u) 2 ( ( ) ( ( )) ( ) ( ( ))) u/2 sin sin 2u/2 sin cos sinh 2u/2 cos 4 4 4 4 ( ( )) ( ( )) Re Z (u) = cos 2u/2 sin cosh 2u/2 cos 4 4 ( ( ) ( /2 ( )) ( ) ( /2 ( ))) /2 sin 4 + sin 4 sinh 2u cos u cos 4 sin 2u 4 ( ( )) ( ( )) Im Z (u) = cos 2u/2 sin cosh 2u/2 cos 4 4

coth (i u) 2

2.2.2
[6]

Anomalous diusion impedance

Z() = Rd

coth (i d ) (i d )
/2

/2

1/2

, 1 ( 2 D )1/

Z() coth (i u) Z(u) = = , u = d , d = 1/2 Rd (i u)

uc 22.3

18CHAPTER 2. MASS TRANSFER BY DIFFUSION, RESTRICTED DIFFUSION

1.2

0.9 Im Z 0.6

uc 0.3

5.1

0 0 4 13 Re Z 2 0.6

Figure 2.5: Nyquist diagram of the reduced modied restricted diusion impedance,
plotted for = 0.8. uc depends on [7].

The D unit (D/cm2 s ) depends on . ( ( ) ( ( )) ( ) ( ( ))) u 2 1 cos sin 2u/2 sin sin sinh 2u/2 cos 4 4 4 ( ( )) ( 4 ( )) cos 2u/2 sin 4 cosh 2u/2 cos 4 ( ( ) ( ( )) ( ) ( ( ))) u 2 1 sin sin 2u/2 sin + cos sinh 2u/2 cos 4 4 4 4 ( ( )) ( ( )) Im Z (u) = cos 2u/2 sin cosh 2u/2 cos 4 4 (Fig. 2.6)

Re Z (u) =

2.3

Cylindrical diusion
Id/21 ( i u) I0 ( i u) = Z (u) = i u Id/2 ( i u) i u I1 ( i u)

d = 2, : cylinder radius

u0

lim Z (u) =

1 2i , lim i u Z (u) = 1 4 u u

u = d , d = 2 /D

2.4

Spherical diusion

d = 3, : sphere radius

2.4. SPHERICAL DIFFUSION

19

Im Z

0.5 u 5

Im Z 0.4 0.6 1 2 4 0 Re Z 0.5 0 0 Re Z 0.5

u0

Figure 2.6: Nyquist diagram of the reduced anomalous diusion impedance. Left:
= 0.8, right: change of Nyquist diagram with ( : 1, 0.9, 0.8, 0.7, 0.6). Dots: u = 5 [6].

Id/21 ( i u) I1/2 ( i u) 1 Z (u) = = = i u Id/2 ( i u) i u I3/2 ( i u) 1 + i u coth i u

lim Z (u) =

1 3i , lim i u Z (u) = 1 5 u u u = d , d = 2 /D, = 2 u 2 cos() 2 cosh() + sin() + sinh() cos() + (2 + 2 ) cosh() 2 (sin() + sinh())

Re Z () = Im Z () =

(2 +

2)

(sin() sinh()) (2 + 2 ) cos() + (2 + 2 ) cosh() 2 (sin() + sinh())

2.4.1

Randles circuit for restricted linear diusion

Impedance coth i u Zf (u) Zf (u) = Rct +Rd , u = d , d = 2 /D , Z(u) = 1 + i (u/d ) Cdl Zf (u) iu

20CHAPTER 2. MASS TRANSFER BY DIFFUSION, RESTRICTED DIFFUSION

Cdl

Rct ZM

Figure 2.7: Randles circuit for restricted diusion.

Chapter 3

Gerischer and diusion-reaction impedance

3.1
3.1.1

Gerischer and modied Gerischer impedance

Gerischer impedance
ZG (u) =

1 1 + iu

In view of the earliest derivation of such an impedance by Gerischer, [14] it seems a good idea to name it the Gerischer impedance ZG [32, 33].

uc

3 u 1

Im ZG

0 0 Re ZG 3 8 1

Figure 3.1: Reduced Gerischer impedance. Some caracteristic values are given in [19].
Phase angle for dashed lines : /8, /6 and /4 respectively.

u0

lim ZG (u) = 1, lim

i u ZG (u) = 1

21

22CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE cos( = arctan(u) ) 1 + u2 + u1 2 = 1/4 2 1 + u2 u (1 + u2 )

Re

ZG (u)

arctan(u) ) 1 + u2 u1 2 = Im ZG (u) = 1/4 2 1 + u2 u (1 + u2 ) 2 + 1 + u2 u dIm ZG (u) = = 0 uc = 3 du 1 2 2 1 + u2 1 + u2 u (1 + u2 ) u sin(

3.1.2

Modied Gerischer impedance #1

1 ZG (u) = 1 + (i u)
0.4 Im ZG 0 0 0.5 Re ZG 1

3 uc

3 uc 3 uc 1 0.75

2 0.5

0 0.5

0.75

Figure 3.2: Reduced modied Gerischer impedance. = 0.5, 0.6, 0.7, 0.8, 0.9, 1. The
line thickness increases with . Dots: characteristic frequency uc at the apex of the impedance arc. Change of uc for the modied Gerischer impedance (solid line) and change of 3/ with (dashed line). uc 3/ for [0.53, 1] (|(uc 3/)|/uc < 5%).

Re ZG (u) =

cos( 1 arctan( 2

u sin( 2 ) )) 1 + u cos( 2 ) ( )1 1 + u2 + 2 u cos( 2 ) 4

u sin( 2 ) )) 1 + u cos( 2 ) Im ZG (u) = ( )1 1 + u2 + 2 u cos( 2 ) 4 sin( 1 arctan( 2

3.1. GERISCHER AND MODIFIED GERISCHER IMPEDANCE

23

3.1.3

Modied Gerischer impedance #2

(1 + i u) ( ) ( )/4 1 Re ZG2 (u) = u2 + 1 cos arctan(u) 2 ( ) ( 2 )/4 1 Im ZG2 (u) = u + 1 sin arctan(u) 2
0.4 Im ZG2
ZG2 (u) =

1
/2

0 0 0.5 Re ZG2 1

3 uc 2 3 0.5 0.75 1

Figure 3.3: Reduced modied Gerischer impedance #2. = 0.5, 0.6, 0.7, 0.8, 0.9, 1.
The line thickness increases with . Dots: characteristic frequency uc at the apex of the impedance arc. Change of uc for the modied Gerischer impedance #2.

24CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE

3.2
3.2.1

Diusion-reaction impedance
Reduced impedance #1

tanh i u + Z (u) = iu + tanh lim Z (u) = 1, lim i u + Z (u) = coth u u0 tanh i u 1 0 Z (u) ZW (u) = , Z (u) ZG (u/) = iu 1 + i u/
0.5 Im Z log uc 3 2 1 log 2.541 0 0 0.5 Re Z 1 0 2 0 log 2

Figure 3.4: Diusion-reaction reduced impedance #1. = 103 , 1, 103 . The line
thickness increases with . uc = 2.542, 3.657, 1732. Change of log uc with log for the diusion-reaction reduced impedance #1. 0 uc 2.54, uc 3.

Re Z (u) =

) ( ( )1 ( )1 coth( ) sinh(2 u2 + 2 4 cau ) cau + sin(2 u2 + 2 4 sau ) sau ( ) 1 1 1 (u2 + 2 ) 4 cos(2 (u2 + 2 ) 4 sau ) + cosh(2 (u2 + 2 ) 4 cau )

u u arctan( ) arctan( ) cau = cos( ), sau = sin( ) 2 2 ( ) ( )1 ( )1 coth( ) sin(2 u2 + 2 4 sau ) cau sinh(2 u2 + 2 4 cau ) sau ( ) Im Z (u) = 1 1 1 (u2 + 2 ) 4 cos(2 (u2 + 2 ) 4 sau ) + cosh(2 (u2 + 2 ) 4 cau )

3.2.2

coth tanh (1 + i u) Z (u) = (1 + i u) lim Z (u) = 1, lim (1 + i u) Z (u) = coth u u0 tanh i u/ 1 lim Z (u) = ZW (u/) = , lim Z (u) = ZG (u) = 0 1 + iu i u/

Reduced impedance #2

) ( ( )1 ( )1 coth( ) sinh(2 1 + u2 4 cau ) cau + sin(2 1 + u2 4 sau ) sau ( ) Re Z (u) = 1 1 1 (1 + u2 ) 4 cos(2 (1 + u2 ) 4 sau ) + cosh(2 (1 + u2 ) 4 cau )

3.2. DIFFUSION-REACTION IMPEDANCE

0.5 Im Z log uc 3 2 1 0 0 0.5 Re Z 1 0 log 2 3 0 log 2

25

Figure 3.5: Diusion-reaction reduced impedance #2. = 104 , 1, 103 . The lLine
thickness increases with . uc = 25407, 3.657, 1.732. Change of log uc with log for the diusion-reaction reduced impedance #2. 0 uc 1/(2.54 ), uc 3.

) ( ) arctan(u) arctan(u) cau = cos , sau = sin 2 2 ) 1 ( ( )4 ( )1 coth( ) sin(2 1 + u2 sau ) cau sinh(2 1 + u2 4 cau ) sau ) ( Im Z (u) = 1 1 1 (1 + u2 ) 4 cos(2 (1 + u2 ) 4 sau ) + cosh(2 (1 + u2 ) 4 cau )

26CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE

3.3

Appendix

Table 3.1: Bounded diusion and diusion-reaction impedance. Denomination Reduced Nyquist impedance diagram impedance
1 u 1

Warburg

1 ZW = iu
4 0 0 1 uc 2.541

Bounded diusion

ZW =

tanh i u iu
4 0 0
uc 1

Semi- spherical diusion

Z =

1+

iu
0 0

4 1

Semi- cylindrical diusion

K0 ( i u) Z = i u K1 ( i u)

1 4 uc 0.542 0 0 4 2
uc 3

Gerischer

1 ZG = 1 + iu
4 0 0 1

uc

Modied Gerischer

1 ZG = 1 + (i u)
0 0 4 1

3.3. APPENDIX

27

Denomination

Table 3.2: Restricted diusion impedance. Reduced Nyquist impedance diagram impedance

d=1 1

Restricted linear diusion

ZM,1

13

uc =3.88 13 d=2 1 14 0 0 uc =11.7 14 d=3 1 15 0 0 15 uc =22.3

coth i u = iu

Restricted cylindrical diusion

ZM,2

I0 ( i u) = i u I1 ( i u)

Restricted spherical diusion

ZM,3 =

1 +

1 i u coth i u

28CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE

Table 3.3: Restricted diusion impedance/continued. Denomination Reduced Nyquist impedance diagram impedance

1.2

0.9

Modied linear restricted diusion

Z =

coth (i u) (i u)

/2

Im Z 0.6

/2

uc 0.3

5.1

0 0 4 13 Re Z 2 0.6

Anomalous linear restricted diusion

Z =

coth (i u) (i u)

/2

Im Z

0.5 u 5

1/2

2 0 0 Re Z 4 0.5

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