Handbook

of
Electrochemical Impedance Spectroscopy

0.5
- Im Z*

0
0 0.5 1
Re Z*

DIFFUSION IMPEDANCES

ER@SE/LEPMI
J.-P. Diard, B. Le Gorrec, C. Montella

Hosted by Bio-Logic @ www.bio-logic.info

August 7, 2012
2
Contents

1 Mass transfer by diffusion, Nernst boundary condition 5

1.1 General diffusion equations . . . . . . . . . . . . . . . . . . . . . 5
1.2 Semi-infinite diffusion . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.1 Semi-infinite linear diffusion . . . . . . . . . . . . . . . . . 6
1.2.2 Semi-infinite radial cylindrical diffusion (outside) . . . . . 7
1.2.3 Semi-infinite spherical diffusion . . . . . . . . . . . . . . . 8
1.3 Bounded diffusion condition (linear diffusion) . . . . . . . . . . . 8
1.3.1 Randles circuit . . . . . . . . . . . . . . . . . . . . . . . . 10
1.3.2 Corrosion equivalent circuit . . . . . . . . . . . . . . . . . 10
1.4 Radial cylindrical diffusion . . . . . . . . . . . . . . . . . . . . . . 12
1.4.1 Finite-length diffusion outside a cylinder . . . . . . . . . . 12
1.4.2 Semi-infinite outside a cylinder . . . . . . . . . . . . . . . 12
1.5 Spherical diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.5.1 Finite-length difusion outside a sphere, reduced impedance
#1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.5.2 Finite outside sphere, reduced impedance # 2 . . . . . . . 13
1.5.3 Infinite outside sphere . . . . . . . . . . . . . . . . . . . . 13

2 Mass transfer by diffusion, restricted diffusion 15

2.1 General diffusion equations . . . . . . . . . . . . . . . . . . . . . 15
2.1.1 Internal cylinder and sphere with null radius . . . . . . . 15
2.2 Linear diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.1 Modified restricted diffusion impedance . . . . . . . . . . 17
2.2.2 Anomalous diffusion impedance . . . . . . . . . . . . . . . 17
2.3 Cylindrical diffusion . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.4 Spherical diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.4.1 Randles circuit for restricted linear diffusion . . . . . . . . 19

3 Gerischer and diffusion-reaction impedance 21

3.1 Gerischer and modified Gerischer impedance . . . . . . . . . . . 21
3.1.1 Gerischer impedance . . . . . . . . . . . . . . . . . . . . . 21
3.1.2 Modified Gerischer impedance #1 . . . . . . . . . . . . . 22
3.1.3 Modified Gerischer impedance #2 . . . . . . . . . . . . . 23
3.2 Diffusion-reaction impedance . . . . . . . . . . . . . . . . . . . . 24
3.2.1 Reduced impedance #1 . . . . . . . . . . . . . . . . . . . 24
3.2.2 Reduced impedance #2 . . . . . . . . . . . . . . . . . . . 24
3.3 Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

3
4 CONTENTS
Chapter 1

Mass transfer by diffusion,

Nernst boundary condition

1.1 General diffusion equations

From:  
∂∆c(x, t) ∂ ∂∆c(x, t)
= D x1−d xd−1
∂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 diffusion) and d = 3 to a spherical electrode [5, 25] (Fig. 1.1), it is
obtained, using the Nernstian boundary condition ∆c(rδ ) = 0:
√ √ √ √
∗ ∆J(r0 , i u) Id/2−1 ( i u ρ) Kd/2−1 ( i u) − Id/2−1 ( i u) Kd/2−1 ( i u ρ)
Z (u) ∝ =√ √ √ √ √
∆c(r0 , i u) i u (Id/2 ( i u) Kd/2−1 ( i u ρ) + Id/2−1 ( i u ρ) Kd/2 ( i u))

where u is a reduced frequency and ρ = rδ /r0 . In (z) gives the modified Bessel
function of the first kind and order n and Kn (z) gives the modified Bessel func-
tion of the second kind and order n [38]. In (z) and Kn (z) satisfy the differential
equation:
−y n2 + z 2 + z y ′ + z 2 y ′′ = 0

r0 r0 r∆ r∆ r0

r∆

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

5
6CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

1.2 Semi-infinite diffusion

1.2.1 Semi-infinite linear diffusion
d = 1, ∆c(∞) = 0

Impedance [35, 4]

Figure 1.2: Warburg element [37].

√
(1 − i) σ 2σ σ σ
ZW (ω) = √ = √ , Re ZW (ω) = √ , Im ZW (ω) = − √
ω iω ω ω
1 F
σ= 2 √ , f= , X ∗ : bulk concentration, σ unit: Ω cm2 s−1/2
n F f X ∗ 2 DX RT

Reduced impedance

∗ 1 ω 1 1
ZW (u) = ZW (ω) = √ , u = 2
, Re ZW (u) = √ , Im ZW (u) = − √
iu 2 σ 2u 2u

1
u=1
- Im ZW
*

-А4
0
0 1
*
Re ZW

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].
σ = σO + σR
1.2. SEMI-INFINITE DIFFUSION 7

Cdl

Rct

Figure 1.4: Randles circuit for semi-infinite linear diffusion.

Impedance
√
1 −i ((1 − i) σ + ω Rct )
Z(ω) = = √
1 3
−i ω + (1 − i) σ ω Cdl + ω 2 Cdl Rct
i ω Cdl +
(1 − i) σ
Rct + √
ω
√
σ + ω Rct
Re Z(ω) = √  √ 3

ω 1 + 2 σ ω Cdl + 2 σ 2 ω Cdl 2 + 2 σ ω 2 Cdl 2 Rct + ω 2 Cdl 2 Rct 2
√ 3
−σ − 2 σ 2 ω Cdl − 2 σ ω Cdl Rct − ω 2 Cdl Rct 2
Im Z(ω) = √  √ 3

ω 1 + 2 σ ω Cdl + 2 σ 2 ω Cdl 2 + 2 σ ω 2 Cdl 2 Rct + ω 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 (τf ) and diffusional (τd )
processes” [36] (Fig. 1.5).
Z(u) (1 + i) T (i + u)
Z ∗ (u) = = √
Rct −T 2 u + (1 + i) (−1 + T + i u) u
2
/ 2 σ 2 , T = τd /τf , τf = Rct Cdl


u = τd ω, τd = Rct
 √
3

T 2 − 2 (−1 + u) + 2 u 2
Re Z ∗ (u) = √ √  
2 2 T u (1 − T + u) + 2 u T 2 + (−1 + T )2 u + u3
√ √
2 T (−1 − u) − 2 u 1 − T + u2



∗ T
Im Z (u) = √ √  
2
2 2 T u (1 − T + u) + 2 u T 2 + (−1 + T ) u + u3
1 1 1
lim Re Z ∗ (u) = 1 − + √ , lim Im Z ∗ (u) = − √
u→0 T 2 u u→0 2u

1.2.2 Semi-infinite radial cylindrical diffusion (outside)

d = 2, ∆c(∞) = 0
√
∗ K0 ( i u)
Z (u) = √ √
i u K1 ( i u)
π π
lim −Im Z ∗ (u) = , Re Z ∗ (uc ) = ⇒ uc = 0.542
u→0 4 4
(Fig. 1.6)
8CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

a b
2 2
- Im Z *

- Im Z *
1 1

0 0
0 1 2 3 0 1-1T 2 3
* *
Re Z Re Z

Figure 1.5: a: Nyquist diagram of the reduced impedance for the Randles circuit
(Fig. 1.4). Semi-infinite linear diffusion. T = 1, 2, 5, 10, 16.4822, 102 , 104 . Line thick-
ness 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
А4
- Im Z *

uc =0.542

0
0 А4 2 4
Re Z *

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

1.2.3 Semi-infinite spherical diffusion

d = 3, ∆c(∞) = 0

1
Z ∗ (u) = √ , u = r02 ω/D
1 + iu
√ √
2+ 2u u
Re Z ∗ (u) = √
, Im Z ∗ (u) = − √ √

2 1+ 2u+u 2 1+ 2u+u

(Fig. 1.7)

1.3 Bounded diffusion condition (linear diffusion)

∆c(rδ ) = 0
”Originally derived by Llopis and Colon [20], and subsequently re-derived by
Sluyters [32] and Yzermans [40], Drossbach and Schultz [13], and Schuhmann
[31]” [4].
1.3. BOUNDED DIFFUSION CONDITION (LINEAR DIFFUSION) 9

uc =1

- Im Z *
0.2

0
0 0.5 1
*
Re Z

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

• IUPAC terminology: bounded diffusion [33]

• Finite-length diffusion with transmissive boundary condition [17, 21]

√
tanh i u √
∗
ZW δ
(u) = √ , u = τd ω, τd = δ 2 /D, γ = 2 u
iu
∗
√ ∗
lim ZW δ
(u) = 1, lim i u ZW δ
(u) = 1
u→0 u→∞

∗ sin(γ) + sinh(γ) ∗ sin(γ) − sinh(γ)

Re ZW (γ) = , Im ZW (γ) =
δ
γ (cos(γ) + cosh(γ)) δ
γ (cos(γ) + cosh(γ))

Figure 1.8: Bounded diffusion impedance.

0.5 uc = 2.541
- Im ZW∆

2
u = Π 2
*

-А4
0
0 0.5 1
*
Re ZW∆

Figure 1.9: Nyquist diagram of the reduced bounded diffusion impedance. (u =

π 2 /2 [30]).
10CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

Cdl

Rct
∆

Figure 1.10: Randles circuit for bounded diffusion.

1.3.1 Randles circuit

Impedance
√
tanh i u
Zf (u) = Rct + Rd √ , u = τd ω, τd = δ 2 /D
iu
sin(γ) + sinh(γ) √
Re Zf (γ) = Rct + Rd , γ = 2u
γ (cos(γ) + cosh(γ))
sin(γ) − sinh(γ)
Im Zf (γ) = Rd
γ (cos(γ) + cosh(γ))

√
tanh i u
Rct + Rd √
Zf (u) iu
Z(u) = = √ !
1 + i (u/τd ) Cdl Zf (u) tanh i u
1 + i (u/τd ) Cdl Rct + Rd √
iu

Reduced impedance
(Fig. 1.11)
√
tanh i u
1+ √
Z(u) ρ iu
Z ∗ (u) = = √ !
Rct + Rd 1

T tanh i u
1+ 1 + iuT + iu √
ρ ρ ρ iu
ρ = Rct /Rd , T = τf /τd , τf = 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 √
i u√
Z(u) = , u = τd ω, τd = δ 2 /D (1.1)
tanh i u
Rct + Rd √
iu
1.3. BOUNDED DIFFUSION CONDITION (LINEAR DIFFUSION) 11

2
log Ρ

-2

-4 log T 0

Figure 1.11: Impedance diagram array for the Randles circuit with bounded diffusion
(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) iu √ Rd
Z ∗ (u) = (1 + α) = (1 + α) , α= (1.2)
Rd tanh i u Rct
1+α √
iu
Two limiting cases (Fig. 1.13):
• α ≪ 1:
√
tanh i u
Z ∗ (u) ≈ √ , uc1 = 2.541, quarter of lemniscate, (Fig. 1.8) (1.3)
iu
• α ≫ 1:
α
Z ∗ (u) ≈ √ , uc2 = α2 , quarter of circle, (Fig. 1.7) (1.4)
α+ iu
12CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

Α = 10-2
0.5 Α2 = 2.541

- Im Z *
Α = 102

0
0 0.5 1
*
Re Z

Figure 1.13: Nyquist diagram of the corrosion equivalent circuit. Large black dot :
uc1 = 2.541, small red dot : uc2 = α2 .

1.4 Radial cylindrical diffusion

d = 2 [15] (Fig. 1.1)

1.4.1 Finite-length diffusion outside a cylinder

√ √ √ √
I0 ( i u ρ) K0 ( i u) − I0 ( i u) K0 ( i u ρ)
Z ∗ (u) = √  √ √ √ √ 
Log(ρ) i u I1 ( i u) K0 ( i u ρ) + I0 ( i u ρ) K1 ( i u)

u = r02 ω/D, ρ = rδ /r0

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

0.5
- Im Z*

0
0 0.5 1
Re Z*

Figure 1.14: Central (ρ < 1) and outside (ρ > 1) cylindrical diffusion impedance.
ρ = rδ /r0 = 10−2 , 10−1 , 0.4, 1.01, 2, 5, 20, 100. The line thickness increases with ρ.
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-infinite outside a cylinder

√
K0 ( i u)
lim Z ∗ (u) = √ √
ρ→∞ i u K1 ( i u)
(Fig. 1.6)
1.5. SPHERICAL DIFFUSION 13

1.5 Spherical diffusion

d = 3 [15] (Fig. 1.1)

1.5.1 Finite-length difusion outside a sphere, reduced impedance

#1
(Fig. 1.15)
1
Z ∗ (u) =  √ √  , u = r02 ω/D, ρ = rδ /r0
(1 − 1/ρ) 1 + i u coth( i u (−1 + ρ))

0.5
2
- Im Z*

log uc

0 -1
0 0.5 1 0 1 5 10
Re Z* r

Figure 1.15: Central (ρ < 1) and outside (ρ > 1) spherical diffusion impedance. ρ =
rδ /r0 = 0.1, 0.4, 0.91, 1.1, 2, 5, 50. Line thickness increases with ρ. Dots: reduced char-
acteristic angular frequency: uc = r02 ω/D = 0.3632, 3.095, 289, 275.8, 4.547, 0.6927, 1.
Change of log uc with ρ.

1.5.2 Finite outside sphere, reduced impedance # 2

(Fig. 1.16)

1+δ
Z ∗ (u) = √ √ , u = (rδ − r0 )2 ω/D, δ = (rδ − r0 )/r0
δ + i u coth( i u)

1.5.3 Infinite outside sphere

(Fig. 1.7)
1
lim Z ∗ (u) = √ , u = r02 ω/D
ρ→∞ 1 + iu
√ √
∗ 2+ 2u ∗ u
Re Z (u) = √
, Im Z (u) = − √ √

2 1+ 2u 2 1+ 2u+u
14CHAPTER 1. MASS TRANSFER BY DIFFUSION, NERNST BOUNDARY CONDITION

2
0.5

1
- Im Z*

log uc

log 2.54
0

0 -1
0 0.5 1 -1 0 5 10
Re Z* d

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

Mass transfer by diffusion,

restricted diffusion

2.1 General diffusion equations

From:  
∂∆c(x, t) 1−d ∂ d−1 ∂∆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 diffusion) and d = 3 to a spherical electrode [5, 25] (Fig. 1.1), it is
obtained, using the condition ∆J(rδ ) = 0:
√ √ √ √
∆J(r0 , i u) Id/2−1 ( i u) Kd/2 ( i u ρ) + Id/2 ( i u ρ) Kd/2−1 ( i u)
Z ∗ (u) ∝ = √ √ √ √ √
∆c(r0 , i u) i u (Id/2 ( i u ρ) Kd/2 ( i u) − Id/2 ( i u) Kd/2 ( i u ρ))
Terminology [24]: bounded system [16], finite-space diffusion [1, 2], finite
length diffusion [18], restricted diffusion [10, 9, 12], reflective boundary condi-
tion [27], impermeable boundary [39], impermeable barrier condition [15], im-
permeable surface [11].

2.1.1 Internal cylinder and sphere with null radius

r0 = 0,

∆,d

Figure 2.1: Restricted diffusion impedance. d = 1: thin planar layer, d = 2: cylinder,

d = 3: sphere.

√
∗ Id/2−1 ( 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.
1 id
u → 0 ⇒ Z ∗ (u) ≈ −
d+2 u

C*

∆,d
» R*

Figure 2.2: Low frequency equivalent circuit for restricted diffusion impedance. R∗ =
1/(d + 2), C ∗ = 1/d.

High frequency limit

Fig. 2.3.

1 √
u → ∞ ⇒ Z ∗ (u) ≈ √ , lim i u Z ∗ (u) = 1
iu u→∞

∆,d
»
Figure 2.3: High frequency equivalent circuit for restricted diffusion impedance.

2.2 Linear diffusion

d=1
√ √ √
∗ Id/2−1 ( i u) I−1/2 ( i u) coth i u
Z (u) = √ √ =√ √ = √
i u Id/2 ( i u) i u I1/2 ( i u) iu

1 i √
lim Z ∗ (u) = − , lim i u Z ∗ (u) = 1
u→0 3 u u→∞

√
u = τd ω, τd = δ 2 /D, γ = 2 u

sin(γ) − sinh(γ) sin(γ) + sinh(γ)

Re Z ∗ (γ) = ; Im Z ∗ (γ) =
γ (cos(γ) − cosh(γ)) γ (cos(γ) − cosh(γ))

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 d=2 d=3

1 1 1
- Im Z *

- Im Z *

- Im Z *
uc =3.88

uc =11.7

uc =22.3
13
14
15

0 0 0
0 13 0 14 0 15
* *
Re Z Re Z Re Z *

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

2.2.1 Modified restricted diffusion impedance

√ α
i u replaced by (i u) 2 (α: dispersion parameter) [8, 7, 29]
α
coth (i u) 2
∗
Z (u) = α , u = τd ω, τd = δ 2 /D
(i u) 2
πα
sin 2uα/2 sin πα − cos πα sinh 2uα/2 cos πα








∗ u−α/2 sin 4 4 4 4
Re Z (u) =
cos 2uα/2 sin πα − cosh 2uα/2 cos πα





4 4

cos πα sin 2uα/2 sin πα + sin πα sinh 2uα/2 cos πα

∗ u−α/2 4 4 4 4
Im Z (u) =
cos 2uα/2 sin πα − cosh 2uα/2 cos πα





4 4

2.2.2 Anomalous diffusion impedance

[6]
γ/2
coth (i ω τd )
Z(ω) = Rd 1−γ/2
, γ≤1
(i ω τd )
γ/2 1/γ
δ2

Z(ω) coth (i u)
Z(u)∗ = = 1−γ/2
, u = ω τd , τd =
Rd (i u) D
18CHAPTER 2. MASS TRANSFER BY DIFFUSION, RESTRICTED DIFFUSION

1.2

0.9

- Im Z *
0.6

uc » 5.1
0.3

Π
Π -Α
-Α 2
4
0
0 13 0.6
*
Re Z

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

The D unit (D/cm2 s−γ ) depends on γ.

γ πγ
sin 2uγ/2 sin πγ − sin πγ γ/2 πγ








u 2 −1 cos 4 4 4 sinh 2u

cos 4
Re Z ∗ (u) = πγ


πγ
cos 2uγ/2 sin 4 − cosh 2uγ/2 cos 4
γ
sin πγ γ/2
sin πγ + cos πγ sinh 2uγ/2 cos πγ








∗ u 2 −1 4 sin 2u 4 4 4
Im Z (u) = πγ
− cosh 2uγ/2 cos πγ





cos 2uγ/2 sin 4 4

(Fig. 2.6)

2.3 Cylindrical diffusion

d = 2, δ: cylinder radius
√ √
∗ Id/2−1 ( i u) I0 ( i u)
Z (u) = √ √ =√ √
i u Id/2 ( i u) i u I1 ( i u)

1 2i √
lim Z ∗ (u) = − , lim i u Z ∗ (u) = 1
u→0 4 u u→∞
u = τd ω, τd = δ 2 /D

2.4 Spherical diffusion

d = 3, δ: sphere radius
2.4. SPHERICAL DIFFUSION 19

1
- Im Z *

- Im Z *
0.5
0.4
u=5 0.6
Γ=1

Π
-H2-ΓL
0 4 0
0 0.5 0 0.5
* *
Re Z Re Z

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

√ √
∗ Id/2−1 ( 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

1 3i √
lim Z ∗ (u) = − , lim i u Z ∗ (u) = 1
u→0 5 u u→∞
√
u = τd ω, τd = δ 2 /D, γ = 2 u
2 cos(γ) − 2 cosh(γ) + γ sin(γ) + γ sinh(γ)
Re Z ∗ (γ) =
(−2 + γ2) cos(γ) + (2 + γ 2 ) cosh(γ) − 2 γ (sin(γ) + sinh(γ))
γ (sin(γ) − sinh(γ))
Im Z ∗ (γ) =
(−2 + γ 2 ) cos(γ) + (2 + γ 2 ) cosh(γ) − 2 γ (sin(γ) + sinh(γ))

2.4.1 Randles circuit for restricted linear diffusion

Impedance
√
coth i u Zf (u)
Zf (u) = Rct +Rd √ , Z(u) = , u = τd ω, τd = δ 2 /D
iu 1 + i (u/τd ) Cdl Zf (u)
20CHAPTER 2. MASS TRANSFER BY DIFFUSION, RESTRICTED DIFFUSION

Cdl

Rct
∆
ZM

Figure 2.7: Randles circuit for restricted diffusion.

Chapter 3

Gerischer and
diffusion-reaction
impedance

3.1 Gerischer and modified Gerischer impedance

3.1.1 Gerischer impedance

∗ 1
ZG (u) = √
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 ” [33, 34].

uc = 3
1 u=1
- Im ZG*

0
0 38 1

Re ZG*

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

∗
√ ∗
lim ZG (u) = 1, lim i u ZG (u) = 1
u→0 u→∞

21
22CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE

arctan(u) p√
cos( ) 1 + u−2 + u−1
Re ∗
ZG (u) = 2 = √ √ √
1/4
(1 + u2 ) 2 1 + u−2 u
arctan(u) p√
) sin( 1 + u−2 − u−1
∗
Im ZG (u) = − 2 = − √ √ √
(1 + u2 )1/4 2 1 + u−2 u
√
∗
dIm ZG (u) −2 + 1 + u−2 u √
= = 0 ⇒ uc = 3
du
r
√ √ √ 1√
2 2 1 + u−2 1 + u−2 − u (1 + u2 )
u

3.1.2 Modified Gerischer impedance #1

∗ 1
ZGα (u) = p
1 + (i u)α

0.4
- Im ZGΑ
*

0
0 0.5 1
*
Re ZGΑ
ÈHuc - 3 ΑLuc Ȑ%

3 5
uc

2
3
0
0.5 0.75 1 0.5 0.75 1
Α Α

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

uα sin( π2α )
cos( 12 arctan( ))
∗ 1 + uα cos( π2α )
Re ZGα (u) =
1
1 + u2 α + 2 uα cos( π2α ) 4
uα sin( π2α )
sin( 12 arctan( ))
∗ 1 + uα cos( π2α )
Im ZGα (u) = −
1
1 + u2 α + 2 uα cos( π2α ) 4
3.1. GERISCHER AND MODIFIED GERISCHER IMPEDANCE 23

3.1.3 Modified Gerischer impedance #2

∗ 1
ZGα2 (u) = α/2
(1 + i u)
 

−α/4 1
∗
Re ZGα2 (u) = u2 + 1 cos α arctan(u)
2
 
∗ 2

−α/4 1
Im ZGα2 (u) = − u + 1 sin α arctan(u)
2

0.4
- Im ZGΑ2
*

0
0 0.5 1
*
Re ZGΑ2

3
uc

2
3
0.5 0.75 1
Α

Figure 3.3: Reduced modified Gerischer impedance #2. α = 0.5, 0.6, 0.7, 0.8, 0.9, 1.
The line thickness increases with α. Dots: characteristic frequency uc at the apex of
the impedance arc. Change of uc for the modified Gerischer impedance #2.
24CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE

3.2 Diffusion-reaction impedance

3.2.1 Reduced impedance #1
√ √
λ tanh i u + λ
∗
Z (u) = √ √
tanh λ iu + λ
∗
√ ∗
√ √
lim Z (u) = 1, lim i u + λ Z (u) = λ coth λ
u→0 u→∞
√
∗ ∗ tanh i u 1
λ → 0 ⇒ Z (u) ≈ ZWδ (u) = √ , λ → ∞ ⇒ Z ∗ (u) ≈ ZG
∗
(u/λ) = p
iu 1 + i u/λ

0.5 3
- Im Z *

log uc
2

1
log 2.541
0 0
0 0.5 1 -2 0 2
*
Re Z log Λ

Figure 3.4: Diffusion-reaction reduced impedance #1. λ = 10−3 , 1, 103 . The line
thickness increases with λ. uc = 2.542, 3.657, 1732. Change of log uc with log λ for√the
diffusion-reaction reduced impedance #1. λ → 0 ⇒ uc → 2.54, λ → ∞ ⇒ uc ≈ λ 3.

√ √ 
1
1 
λ coth( λ) sinh(2 u2 + λ2 4 cauλ ) cauλ + sin(2 u2 + λ2 4 sauλ ) sauλ
Re Z ∗ (u) = 1
 1 1

(u2 + λ2 ) 4 cos(2 (u2 + λ2 ) 4 sauλ ) + cosh(2 (u2 + λ2 ) 4 cauλ )

arctan( uλ ) arctan( uλ )
cauλ = cos( ), sauλ = sin( )
2 2
√ √ 
1
1 
λ coth( λ) sin(2 u2 + λ2 4 sauλ ) cauλ − sinh(2 u2 + λ2 4 cauλ ) sauλ
Im Z ∗ (u) = 1
 1 1

(u2 + λ2 ) 4 cos(2 (u2 + λ2 ) 4 sauλ ) + cosh(2 (u2 + λ2 ) 4 cauλ )

3.2.2 Reduced impedance #2

√ √ p
λ coth λ tanh (1 + i u) λ
∗
Z (u) = p
(1 + i u) λ
∗
p √ √
lim Z (u) = 1, lim (1 + i u) λ Z ∗ (u) = λ coth λ
u→0 u→∞
p
∗ tanh i u/λ 1
lim Z (u) = ZWδ (u/λ) = p , lim Z ∗ (u) = ZG
∗
(u) = √
λ→0 i u/λ λ→∞ 1 + iu

√ 
1 √
1 √ 
coth( λ) sinh(2 1 + u2 4 λ cau ) cau + sin(2 1 + u2 4 λ sau ) sau
Re Z ∗ (u) = 1
 1 √ 1 √

(1 + u2 ) 4 cos(2 (1 + u2 ) 4 λ sau ) + cosh(2 (1 + u2 ) 4 λ cau )
3.2. DIFFUSION-REACTION IMPEDANCE 25

0.5 3
- Im Z *

log uc
2

1
log 3
0 0
0 0.5 1 -2 0 2
Re Z * log Λ

Figure 3.5: Diffusion-reaction reduced impedance #2. λ = 10−4 , 1, 103 . The lLine
thickness increases with λ. uc = 25407, 3.657, 1.732. Change of log uc with log λ for
the diffusion-reaction
√ reduced impedance #2. λ → 0 ⇒ uc ≈ 1/(2.54 λ), λ → ∞ ⇒
uc → 3.

   
arctan(u) arctan(u)
cau = cos , sau = sin
2 2
√  1 √
1 √ 
coth( λ) sin(2 1 + u2 4 λ sau ) cau − sinh(2 1 + u2 4 λ cau ) sau


Im Z ∗ (u) = 1
 1 √ 1 √

(1 + u2 ) 4 cos(2 (1 + u2 ) 4 λ sau ) + cosh(2 (1 + u2 ) 4 λ cau )
26CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE

3.3 Appendix

Table 3.1: Bounded diffusion and diffusion-reaction impedance.

Denomination Reduced Nyquist impedance diagram
impedance

1
u=1

∗ = √1
ZW
Warburg
iu
-А4
0
0 1

uc =2.541
√
Bounded ∗ tanh i u
ZW = √
diffusion δ
iu
-А4
0
0 1

uc =1
Semi-∞ 1
spherical Z∗ = √
1+ iu
diffusion 0
-А4
0 1

1
Semi-∞ √ А4
∗ K0 ( i u)
cylindrical Z = √ √ uc =0.542
diffusion i u K1 ( i u)
0
0 А4 2 4

uc = 3

∗ = √ 1
ZG
Gerischer
1 + iu
-А4
0
0 1

uc » 3 Α

Modified ∗ 1
ZGα = p
Gerischer 1 + (i u)α
-ΑА4
0
0 1
3.3. APPENDIX 27

Table 3.2: Restricted diffusion impedance.

Denomination Reduced Nyquist impedance diagram
impedance

d=1
1

Restricted √

uc =3.88
∗ coth i u
linear ZMδ,1 = √
diffusion iu
13

0
0 13

d=2
1

Restricted √
I0 ( i u)
uc =11.7

∗
cylindrical ZMδ,2 =√ √
diffusion i u I1 ( i u)
14

0
0 14

d=3
1

Restricted 1
uc =22.3

∗
spherical ZMδ,3 = √ √
−1 + i u coth i u
diffusion
15

0
0 15
28CHAPTER 3. GERISCHER AND DIFFUSION-REACTION IMPEDANCE

Table 3.3: Restricted diffusion impedance/continued.

Denomination Reduced Nyquist impedance diagram
impedance

1.2

0.9

Modified

- Im Z *
α/2
linear coth (i u)
Z∗ = α/2
0.6
restricted (i u)
diffusion uc » 5.1
0.3

Π
Π -Α
-Α 2
4
0
0 13 0.6
Re Z *

1
- Im Z *

Anomalous
γ/2
linear coth (i u) 0.5
Z∗ = 1−γ/2
restricted (i u)
diffusion u=5

Π
-H2-ΓL
0 4
0 0.5
*
Re Z
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