Handbook of Electrochemical Impedance Spectroscopy

1 if idO

if ifM ifO

1 0.2 Ecorr EV 0.2

0.4 Im Z 1 Rct Cdl 2

Rct Re Z

Rp

CORROSION REACTIONS LIBRARY

J.-P. Diard, C. Montella, N. Murer LEPMI, Bio-Logic Hosted by Bio-Logic @ www.bio-logic.info

July 17, 2012

Contents
1 Reactions without adsorbed species 1.1 Reactions without mass transport limitation 1.1.1 Mechanism . . . . . . . . . . . . . . 1.1.2 Kinetic equations . . . . . . . . . . . 1.1.3 Steady-state conditions . . . . . . . 1.1.4 Faradaic impedance . . . . . . . . . 1.2 Reactions with mass transport limitation . 1.2.1 Mechanism . . . . . . . . . . . . . . 1.2.2 Example: Iron in aerobic solution [4] 1.2.3 Kinetic equations . . . . . . . . . . . 1.2.4 Steady-state conditions . . . . . . . 1.2.5 Faradaic impedance [3] . . . . . . . . 5 5 5 5 5 6 8 8 8 8 8 9 11 11 11 11 12 13 15 15 15 15 16 19 19 19 19 20

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2 Reactions involving one adsorbate 2.1 Volmer-Heyrovsk (V-H) corrosion reaction . . . . . . . y 2.1.1 Mechanism . . . . . . . . . . . . . . . . . . . . . 2.1.2 Kinetic equations . . . . . . . . . . . . . . . . . . 2.1.3 Steady-state conditions . . . . . . . . . . . . . . 2.1.4 Faradaic impedance . . . . . . . . . . . . . . . . 2.2 (V-H) corrosion reaction with mass transport limitation 2.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . 2.2.2 Kinetic equations . . . . . . . . . . . . . . . . . . 2.2.3 Steady-state conditions . . . . . . . . . . . . . . 2.2.4 Faradaic impedance . . . . . . . . . . . . . . . . 2.3 Volmer-Tafel (V-T) corrosion reaction . . . . . . . . . . 2.3.1 Mechanism . . . . . . . . . . . . . . . . . . . . . 2.3.2 Kinetic equations . . . . . . . . . . . . . . . . . . 2.3.3 Steady-state conditions . . . . . . . . . . . . . . 2.3.4 Faradaic impedance . . . . . . . . . . . . . . . .

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CONTENTS

Chapter 1

Electrochemical reactions without adsorbed species

1.1
1.1.1

Electrochemical reactions without mass transport limitation

Mechanism
o1 M Mn1 + + n1 e

r2 O + n2 e R

1.1.2

Kinetic equations

Butler-Volmer kinetic, kinetic irreversibility of electrochemical reactions (kr1 = ko2 = 0), no mass transport limitation (O(0, t) = O ). Ko1 = ko1 exp (o1 n1 f E) , Kr2 = kr2 exp (r2 n2 f E) , f = F/(R T ) Current density vs. step rates if (t) = F (n1 v1 (t) n2 v2 (t)) Step rates v1 (t) = Ko1 (t), v2 (t) = Kr2 (t) O

1.1.3

Steady-state conditions
v1 = Ko1 , v2 = Kr2 O

Step rates

Current density if = F (n1 Ko1 n2 Kr2 O ) 5 (1.1)

CHAPTER 1. REACTIONS WITHOUT ADSORBED SPECIES

1.1.4

Faradaic impedance
Zf (s) = Rct (1.2)

Faradaic impedance

Charge transfer resistance Rct = Polarization resistance Rp = Rct Relation between Rct , Rp and icorr Rct (Ecorr ) = Rp (Ecorr ) = icorr = Stern-Geary relationship [5]. Electrode impedance Z(s) = Zf (s) Rct = 1 + s Cdl Zf (s) 1 + s Cdl Rct (1.4) 1 f F (n2 O Kr2 (Ecorr ) r2 + n2 Ko1 (Ecorr ) o1 ) 2 1 1 f (o1 n1 + r2 n2 ) Rct (Ecorr ) 1 f F (n2 O Kr2 r2 + n2 Ko1 o1 ) 2 1 (1.3)

icorr

Im Z

icorr if

if ifM ifO

c 1 Rct Cdl

0 Ecorr E

0 Re Z

Rp

Rct

Figure 1.1: Typical if vs. E curve calculated with Eq. (1.1) and Nyquist impedance
diagram calculated at the corrosion potential with Eqs. (1.3)-(1.4).

1.1. REACTIONS WITHOUT MASS TRANSPORT LIMITATION Equivalent circuit

Cdl

Rct

Figure 1.2: Equivalent circuit of the electrode impedance (Eq. (1.4)).

CHAPTER 1. REACTIONS WITHOUT ADSORBED SPECIES

1.2
1.2.1

Electrochemical reactions with mass transport limitation

Mechanism
o1 M Mn1 + + n1 e

r2 O + n2 e R

1.2.2

Example: Iron in aerobic solution [4]

Fe Fe2+ + 2e O2 +2H2 O + 4e 4OH

1.2.3

Kinetic equations

Butler-Volmer kinetic, kinetic irreversibility of electrochemical reactions (kr1 = ko2 = 0), mass transport limitation. Ko1 = ko1 exp (o1 n1 f E) , Kr2 = kr2 exp (r2 n2 f E) , f = F/(R T ) Mass balance equations Flux of soluble species JO (0, t) = v2 (t) Current density vs. step rates if (t) = F (n1 v1 (t) n2 v2 (t)) Step rates v1 (t) = Ko1 (t), v2 (t) = Kr2 (t) O(0, t)

1.2.4

Steady-state conditions

Steady-state equations Soluble species JO (0) = mO (O O(0))

1/3 2/3

mO = DO /O , O = 1, 611 DO 1/6 1/2 , mO = 0, 620 DO 1/6 1/2 Steady-state solutions Soluble species O(0) = Current density O mO Kr2 + mO (1.5)

( ) n2 O Kr2 mO if = F n1 Ko1 Kr2 + mO

1.2. REACTIONS WITH MASS TRANSPORT LIMITATION if = ifM + ifO , ifM = n1 F Ko1 , ifO = idO =
E

n2 F O Kr2 mO Kr2 + mO lim if = n2 F O mO

1.2.5

Faradaic impedance [3]

Zf (s) = Rct + ZO (s) (1.6)

Faradaic impedance

Charge transfer resistance Rct = 1 f F (n2 O(0) Kr2 r2 + n2 Ko1 o1 ) 2 1 (1.7)

Concentration impedance Soluble species ZO (s) =

2 Rct n2 O(0)MO (s)Kr2 r2 2 2 O(0)K + n2 K (M (s)K n2 O r2 r2 r2 1 o1 o1

MO (s) =

1 th dO s O , dO = mO dO s DO th dO s dO s , ZO (s) = kO th dO s 1+ dO s

+ 1)

(1.8)

2 Rct n2 O(0)Kr2 r2 o1 n2 Ko1 Kr2 2 1 , kO = mO (o1 n2 Ko1 + O(0) r2 n2 Kr2 ) mO (o1 n2 Ko1 + r2 n2 Kr2 O(0)) 2 2 1 1 kO RO (s) = lim ZO (s) = s0 1+

Polarization resistance ( ) 2 n2 O(0)Kr2 r2 2 Rp = Rct 1 + 2 n2 O(0)Kr2 mO r2 + n2 Ko1 o1 (Kr2 + mO ) 1 Relation between Rct , Rp and icorr Rct (Ecorr ) = 1 f F (n2 O(0, Ecorr ) Kr2 (Ecorr ) r2 + n2 Ko1 (Ecorr ) o1 ) 2 1 1 icorr = f (o1 n1 + r2 n2 ) Rct (Ecorr ) 1 ( )) = ( mO f o1 n1 + r2 n2 Rp (Ecorr ) mO + Kr2 (Ecorr ) 1 = idO f o1 n1 Rp (Ecorr )

icorr Limiting case

ko1 Ecorr icorr

10

CHAPTER 1. REACTIONS WITHOUT ADSORBED SPECIES

Electrode impedance Z(s) = Equivalent circuit Zf (s) 1 + s Cdl Zf (s) (1.9)

Cdl

Cdl

O Rct ZO Rct R'O

Figure 1.3: Equivalent circuits of the electrode impedance (Eq. (1.9)). ZWO =
th dO s RdO , RdO = kO , RO = kO /. dO s

1 if idO

if ifM ifO Im Z

0.5

1 Rct Cdl

1 0.2 Ecorr EV 0.2 0

2.54

0 Re Z

Rct

Rp

1 if idO

if ifM ifO Im Z

0.4 1 Rct Cdl 2

1 0.2 Ecorr EV 0.2

Rct Re Z

Rp

Figure 1.4: Typical if vs. E curve calculated with Eq. (1.5) and Nyquist impedance
diagrams calculated at the corrosion potential with Eqs. (1.6)-(1.8) [2, 1].

Chapter 2

Electrochemical reactions involving one adsorbate

2.1
2.1.1

Volmer-Heyrovsk (V-H) corrosion reaction y

Mechanism
r1 H+ + s + e H,s

r2 H+ + H,s + e H2 + s

o3 M,s M2+ + s + 2 e

2.1.2

Kinetic equations
H + (0, t) H + , M, s s
Kr1 = kr1 exp (r1 f E) , kr1 = kr1 H +

No mass transport limitations, Langmuir isotherm

Kr2 = kr2 exp (r2 f E) , kr2 = kr2 H + , Ko3 = ko3 exp (2 o3 f E)

Transformation rates vs (t) = v1 (t) + v2 (t), vH (t) = v1 (t) v2 (t) Mass balance equations Rate of production of adsorbed species ds (t) vs (t) dH (t) vH (t) = , = dt dt Current density vs. step rates if (t) = F (v1 (t) + v2 (t) 2 v3 (t)) 11

12 Step rates

CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE

v1 (t) = Kr1 (t) s (t), v2 (t) = Kr2 (t) H (t), v3 (t) = Ko3 (t) s (t)

2.1.3

Steady-state conditions

Steady-state equations Adsorbed species ds /dt = 0, H + s = 1 Steady-state solutions Adsorbed species s = Current density if = 2 F (Ko3 Kr2 Kr1 Kr2 ) Kr1 + Kr2 1 = ln (r1 + 2 o3 ) f ( kr1 ko3 ) (2.1) Kr1 Kr2 , H = Kr1 + Kr2 Kr1 + Kr2

if = 0 E = Ecorr

icorr =

2 F Ko3 (Ecorr ) Kr2 (Ecorr ) 2 F Kr1 (Ecorr ) Kr2 (Ecorr ) = Kr1 (Ecorr ) + Kr2 (Ecorr ) Kr1 (Ecorr ) + Kr2 (Ecorr ) 2 F kr1 kr2 = r2 r1 ( ( ) ) kr1 2o3 + r1 kr1 2o3 + r1 + kr2 kr1 ko3 ko3

0.02

if A cm

0.02 0.4 0.2 E V Ecorr

ko3 = 101 s1 , r1 = 0.8, r2 = 0.3, o3 = 0.4, = 109 mol cm2 , f = 38.9 V1 , F = 96485 C mol1 .

Figure 2.1: if vs. E curve calculated with Eq. (2.1) for kr1 = 1 s1 , kr2 = 1 s1 ,

 2.1. VOLMER-HEYROVSKY (V-H) CORROSION REACTION

13

2.1.4

Faradaic impedance
Zf (s) = Rct + ZH (s) + Zs (s)

Faradaic impedance

Zf (s) = (Kr2 + Kr1 )(Kr2 + Kr1 + s) f F Kr2 (r1 Kr1 (2(Ko3 + Kr2 ) + s) + 4o3 Ko3 (Kr2 + Kr1 + s) + r2 Kr1 (2Ko3 + 2Kr1 + s)) Charge transfer resistance Rct = 1 Kr2 + Kr1 = f F (r2 H Kr2 + (4 o3 Ko3 + r1 Kr1 ) s ) f F Kr2 (4 o3 Ko3 + (r1 + r2 ) Kr1 )

Polarization resistance Rp = (Kr2 + Kr1 )2 2 f F Kr2 (2 o3 Ko3 (Kr2 + Kr1 ) + Kr1 (r1 (Ko3 + Kr2 ) + r2 (Kr1 Ko3 )))

No simple relation between Rp and icorr .

Relation between Rct and icorr Rct (Ecorr ) = 1 f F (r2 H (Ecorr ) Kr2 (Ecorr ) + (4 o3 Ko3 (Ecorr ) + r1 Kr1 (Ecorr )) s (Ecorr )) icorr = 1 (2 o3 + (r1 + r2 )/2) f Rct (Ecorr )

14

CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE

Z 0.5 Im Z Rp Zf

Ecorr Im Z Rp

0.5

Z Zf

E V

Ecorr 0.04

0 0 0.5 Re Z Rp 1 Rct Rp

0 0 0.5 Re Z Rp Rct Rp 1

E 0 log Z Rp

Ecorr log Z Rp 0

Z Zf

E V

Ecorr 0.04

Zf 1 2 Z 0 2 log rad s 4

0.2 0 log rad s 5

Figure 2.2: Two typical Nyquist impedance and Bode diagrams for the VolmerHeyrovsk (V-H) corrosion reaction (Thick lines: Faradaic impedance, thin lines: y electrode impedance). Parameters value as in Fig. 2.1 and Cdl = 105 F.

2.2. (V-H) CORROSION REACTION WITH MASS TRANSPORT LIMITATION15

2.2
2.2.1

Volmer-Heyrovsk (V-H) corrosion reaction y with mass transport limitation

Mechanism
r1 H+ + s + e H,s

r2 H+ + H,s + e H2 + s

o3 M,s M2+ + s + 2 e

2.2.2

Kinetic equations

Butler-Volmer kinetic, Langmuir isotherm, with mass transfer limitation, M, s s. Kr1 = kr1 exp (r1 f E) , Kr2 = kr2 exp (r2 f E) , Ko3 = ko3 exp(o3 2 f E), f = F/(R T ) Mass balance equations Flux of soluble species JH+ (0, t) = v1 (t) v2 (t) Rate of production of adsorbed species ds (t) v1 (t) + v2 (t) dH (t) v1 (t) v2 (t) = , = dt dt Current density vs. step rates if (t) = F (v1 (t) + v2 (t) 2 v3 (t)) Step rates v1 (t) = Kr1 (t) H + (0, t) s (t), v2 (t) = Kr2 (t) H + (0, t) H (t), v3 (t) = Ko3 (t) s (t)

2.2.3

Steady-state conditions

Steady-state equations Soluble species JH+ (0) = mH+ (H + H + (0)) mH+ = DH+ /H+ , H+ = 1, 611 DH+ 1/6 1/2 , mH+ = 0, 620 DH+ 1/6 1/2
1/3 2/3

Adsorbed species ds /dt = 0, H + s = 1

16

CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE

Steady-state solutions Soluble species H + (0) = H +* (Kr1 + Kr2 ) mH+ , 2Kr1 Kr2 + (Kr1 + Kr2 ) mH+

Adsorbed species s = Kr1 Kr2 , H = Kr1 + Kr2 Kr1 + Kr2

Current density ( ( ) ) 2F Kr2 mH+ (Kr1 + Kr2 ) Ko3 H +* Kr1 + 2Ko3 Kr1 Kr2 if = (Kr1 + Kr2 ) (mH+ (Kr1 + Kr2 ) + 2Kr1 Kr2 )

(2.2)

0.04 if A cm
2

0.04 0 0.1 EV 0.2 0.3

kr2 = 107 mol1 cm3 s1 , ko3 = 102 s1 , r1 = 0.8, r2 = 0.3, o3 = 0.5, DH+ = 106 cm2 s1 , = 102 cm2 s1 , = 100 rpm, = 109 mol cm2 , f = 38.9 V1 , F = 96485 C mol1 .

Figure 2.3: if vs. E curve calculated with Eq. (2.2) for kr1 = 107 mol1 cm3 s1 ,

2.2.4

Faradaic impedance

Faradaic impedance Zf (s) = Rct + ZH+ (s) + Z (s), Z (s) = Zs (s) + ZH+ (s) Zf (s) = af1 + saf2 + af3 MH+ (s) + saf4 MH+ (s) bf1 + sbf2 + bf3 MH+ (s) + sbf4 MH+ (s)

af1 = (Kr1 + Kr2 ) H + (0), af2 = 1, af3 = 2Kr1 Kr2 H + (0), af4 = (Kr2 H + Kr1 s ) ( ( ) ( ( ) )) bf1 = 2f F H + (0) H Kr2 r2 Kr1 H + (0) Ko3 + s Kr1 r1 Kr2 H + (0) + Ko3 + 2Ko3 o3 (Kr1 + Kr2 ) ( ) bf2 = f F H Kr2 r2 H + (0) + Kr1 r1 s H + (0) + 4Ko3 o3 s bf3 = 4f F 2 Ko3 Kr1 Kr2 s H + (0) (H (r1 r2 ) + 2o3 ) , bf4 = 4f F 2 Ko3 o3 s (H Kr2 + Kr1 s )

2.2. (V-H) CORROSION REACTION WITH MASS TRANSPORT LIMITATION17 Charge transfer resistance Rct = 1 f F (H Kr2 r2 H + (0) + Kr1 r1 s H + (0) + 4Ko3 o3 s )

Polarization resistance Rp = (mH + (Kr1 + Kr2 ) + 2Kr1 Kr2 ) / ( ( ) ( ( ) ( ( 2f F mH + H Kr2 r2 Kr1 H + (0) Ko3 + s Kr1 r1 Kr2 H + (0) + Ko3 +2Ko3 o3 (Kr1 + Kr2 ))) + 2Ko3 Kr1 Kr2 s (H (r1 r2 ) + 2o3 ))) No simple relation between Rp and icorr .

Relation between Rct and icorr Rct (Ecorr ) = f F (H (Ecorr )Kr2 (Ecorr )r2 H + (0, E 1 + corr ) + Kr1 (Ecorr )r1 s (Ecorr )H (0, Ecorr ) + 4Ko3 (Ecorr )o3 s (Ecorr ))

icorr =

1 (2 o3 + (r1 + r2 )/2) f Rct (Ecorr )

18

CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE

Z 0.5 Im Z Rp Zf

Ecorr Im Z Rp

0.5

Z Zf

E V

Ecorr 0.06

0 0 0.5 Re Z Rp 1

0 0 0.5 Re Z Rp 1

Z Zf log Z Rp 0

Ecorr log Z Rp 0

Z Zf

E V

Ecorr 0.06

0.2 0 log rad s 5

0.2 0 log rad s 5

Figure 2.4: Two typical Nyquist impedance and Bode diagrams for the VolmerHeyrovsk (V-H) corrosion reaction with mass transport limitation (Thick lines: y Faradaic impedance, thin lines: electrode impedance). Parameters value as in Fig. 2.3 and Cdl = 5 105 F.

2.3. VOLMER-TAFEL (V-T) CORROSION REACTION

19

2.3
2.3.1

Volmer-Tafel (V-T) corrosion reaction

Mechanism
r1 H+ + s + e H,s

d2 2 H,s H2 + 2 s o3 M,s M2+ + s + 2 e

2.3.2

Kinetic equations

No mass transport limitations, Langmuir isotherm, H + (0, t) H + , M, s s, Kr1 = kr1 exp (r1 f E) , kr1 = kr1 H + Ko3 = ko3 exp (2 o3 f E) , ko1 = 0, kr3 = 0. Mass balance equations Rate of production of adsorbed species ds (t) v1 (t) + 2 v2 (t) dH (t) v1 (t) 2 v2 (t) = , = dt dt Current density vs. step rates if (t) = F (v1 (t) 2 v3 (t)) Step rates v1 (t) = Kr1 (t) s (t), v2 (t) = kd2 ( H (t))2 , v3 (t) = Ko3 (t) s (t)

2.3.3

Steady-state conditions

Steady-state equations Adsorbed species ds /dt = 0, H + s = 1 Steady-state solutions Adsorbed species 4kd2 + Kr1 Kr1 8kd2 + Kr1 s = , s + H = 1 4kd2 Current density 4F 2 kd2 (2Ko3 Kr1 ) 4kd2 + Kr1 + Kr1 8kd2 + Kr1 ( ) 1 kr1 if = 0 E = Ecorr = log f (2o3 + r1 ) 2ko3 if = (2.3)

20

CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE ( ) 23exp2 F 2 kd2 ko3 ko3 exp2 kr1 ( ) ( ) exp1 ko3 exp1 k + 4kd2 + 2 2exp1 kr1 ko3 exp1 + 8kd2 r1 kr1 kr1 r1 2o3 , exp2 = 2o3 + r1 2o3 + r1

icorr = 2exp1 kr1 with

ko3 kr1

exp1

exp1 =

0.05
2

if mA cm

0.4

0.2 E V

Ecorr

mol1 cm2 s1 , ko3 = 101 s1 , r1 = 0.7, o3 = 0.4, n3 = 1, = 109 mol cm2 , f = 38.9 V1 , F = 96485 C mol1 .

Figure 2.5: if vs. E curve calculated with Eq. (2.3) for kr1 H + = 103 s1 , kd2 = 108

2.3.4

Faradaic impedance
Rct = 1 f F (4Ko3 o3 + Kr1 r1 ) s

Transfer resistance

Concentration impedance Zs (s) = Kr1 (Kr1 2Ko3 ) Rct r1 2Ko3 Kr1 r1 + Kr1 (s + 4kd2 H ) r1 + 4Ko3 o3 (s + Kr1 + 4kd2 H )

Faradaic impedance ( 1+ Zf (s) = Rct + Zs (s) Kr1 (Kr1 2Ko3 ) r1 2Ko3 Kr1 r1 + Kr1 (s + 4kd2 H ) r1 + 4Ko3 o3 (s + Kr1 + 4kd2 H ) )

Zf (s) = Rct

Polarization resistance ( ) Kr1 (Kr1 2Ko3 ) Rct r1 Rp = Rct 1 + 2Ko3 Kr1 (2o3 + r1 ) + 4kd2 (4Ko3 o3 + Kr1 r1 ) H No simple relation between Rp (Ecorr ) and icorr . Relation between Rct (Ecorr ) and icorr icorr = 1 f (2o3 + r1 ) Rct (Ecorr )

2.3. VOLMER-TAFEL (V-T) CORROSION REACTION Equivalent circuit Zs = Rs = Rs 4Ko3 o3 + Kr1 r1 , Cs = 1 + Rs Cs s Kr1 (Kr1 2Ko3 ) Rct r1

21

Kr1 (Kr1 2Ko3 ) Rct r1 2Ko3 Kr1 (2o3 + r1 ) + 4kd2 (4Ko3 o3 + Kr1 r1 ) A

Z Zf Im Z Rp

Ecorr

Z Zf Im Z Rp 0.45

E V

Ecorr 0.04

0.45

0 0 0.5 Re Z Rp 1

0 0 0.5 Re Z Rp 1

E 0 log Z Rp

Ecorr 0 log Z Rp

E V

Ecorr 0.04

Zf 1 2 Z 0 log rad s 2 0.5 2

Zf Z 0 log rad s 2

Figure 2.6: Two typical Nyquist impedance and Bode diagrams for the VolmerTafel (V-T) corrosion reaction (Thick lines: Faradaic impedance, thin lines: electrode impedance). Parameters value as in Fig. 2.5 and Cdl = 1 105 F.

22

CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE

Cdl

Cs

Rct Rs

Figure 2.7: Equivalent circuit for the impedance of (V-T) corrosion reaction.

Bibliography
[1] Diard, J.-P., B. Le Gorrec, and Montella, C. Handbook of electrochemical impedance spectroscopy. Diusion Impedances. www.bio-logic.info/potentiostat/notes.html (2012). [2] Macdonald, J. R. Impedance spectroscopy: old problems and new developments. Electrochim. Acta 35 (1990), 14831492. [3] Montella, C., Diard, J.-P., and B. Le Gorrec. Exercices de cintique e lectrochimique. II. Mthode dimpdance. Hermann, Paris, 2005. e e e [4] Orazem, M. E., and Tribollet, B. Electrochemical impedance spectroscopy. John Wiley & Sons, Hoboken, 2008. [5] Stern, M., and Geary, A. J. Electrochemical polarization. I. A theoretical analysis of the shape of polarization curves. J. Electrochem. Soc 104 (1957), 5663.

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