Chapter 4

Electrochemical kinetics at electrode / solution

interface and electrochemical overpotential
 0. Brief introduction
1) Two important empirical relations
(2) Nernst equation:
c d
RT a a
EE  ln C
a
D
b
nF a a A B

RT aox RT
   ln    ln  ai i
nF ared nF i

Dependent of electrode potential on species activities

Valid only for reversible cell or for electrode at

electrochemical reversibility.
inet =0
 0. Brief introduction
1) Two important empirical relations
(2) Tafel equation:

 = a + b log j

The point of intersection of the extrapolation on the

line  = 0 is log i0.

A is in fact the  at j = 1 A cm-2.

Valid only for special irreversible process when 

> 118 mV.
 Chapter 4 Electrochemical kinetics at electrode

Effect of potential on electrode reaction

1. Thermodynamic aspect

If electrode reaction is fast and electrochemical equilibrium

remains, i.e., Nernst equation is applicable. Different
potential corresponds to different surface concentration—
concentration/diffusion control.
2. Kinetic aspect

If electrode reaction is slow and electrochemical equilibrium

is broken. Different potential corresponds to different
activation energy—activation/electrochemistry control.
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
4.1.1 basic concepts
For Elementary unimolecular opposing
process
rf  k f c A
Rate expressions rb  kb cB
rnet  rf  rb  k f c A  kb cB

rnet  0;
kb (cB )eq  k f (c A )eq
Exchange rate of reaction
At equilibrium kf (cB )eq
K  Kinetic equilibrium
kb (c A )eq
constant
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
4.1.1 basic concepts
For electrochemical reactions:
if ic
rf   k f cA ; rc   k f cOx ic  k f nFAcOx
nFA nFA
At equilibrium conditions: ia  k f nFAcRe d

inet  ic  ia
i0  ic ,0  ia ,0
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
Some important empirical formula:

 Ea 
Arrhenius equation k  A exp   
 RT 
According to Transition State Theory:

kT 
k  K
h
Corresponding to steric factor in
kT  G   SCT
k  exp   
h  RT  kT/h term corresponds to the frequency
factor
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
In electrochemistry,
electrochemical potential
was used instead of
chemical potential (Gibbs
free energy)

Potential curve described by Morse empirical equation

  Red
kf

Ox  ne 
kb
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
4.1.2 net current and exchange current


kc

Ox  ne   Red
ka

ic  nFAkc cOx (0, t )

ia  nFAka cRed (0, t )

Net current: i  ic  ia  nFA[kc cOx (0, t )  ka cRed (0, t )]

 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
i  ic  ia  nFA[kc cOx (0, t )  ka cRed (0, t )]
If cOx = cRed = activity = 1 at re
At equilibrium condition
Then i net = 0 i0  ic ,0  ia ,0 standard exchange current

Gc
kT  RT
kc   e
h

Ga
kT  RT
ka   e
h
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy

For unequilibrium conditions

 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
4.1.3 effect of overpotential on activation energy

transfer coefficient

polarization   ir  re ΔG  nFE  nFΔ

ΔG  ΔG0  nFΔ
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
Ox  ne Red
c ,re

ΔGc,0  nFΔ
ΔGa,0 nFΔ
 nFΔ
 ΔGa
ΔG
c
c ,ir a ,ir
Fraction of applied potential
FΔ F  Δ alters activation energy  for
F Δ oxidation and  for reduction

Anode side Ga  Ga,0   nFΔ

cathode side Gc  Gc,0   nFΔ

 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
 0
tan  FE / x
 nFΔ tan   (1   ) FE / x
  tan 
  
 tan   tan
x
 nFΔ  is usually approximate to 1/2
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
4.1.4 Effect of polarization on reaction rate
Marcus theory: transition state theory
k BT Gc ,0   nF 


kc   c exp( )
h RT
k BT G 
 nF 
 c exp( c ,0
) exp( )
h RT RT
 nF 
 kc ,0 exp( )
RT

k BT Ga,0   nF 
ka   a exp( )
h RT
 nF 
 ka ,0 exp( )
RT
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy
 nF 
ic  kc cOx (0, t )  nFcOx (0, t )kc ,0 exp( )
RT
No concentration polarization

 nF   nF 
ic  ic ,0 exp( ) ia  ia ,0 exp( )
RT RT

2.3RT 2.3RT
 lg ic ,0  lg ic
If initial potential  nF  nF
is 0, then
2.3RT 2.3RT
 lg ia ,0  lg ia
 nF  nF
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy

2.3RT 2.3RT
c  re     lg ic ,0  lg ic
 nF  nF

2.3RT 2.3RT
a    re   lg ia ,0  lg ia
 nF  nF

At equilibirum
2.3RT ic
ia,0  ic,0  i0 c  lg
 nF i0

2.3RT ia
a  lg
 nF i0
 Chapter 4 Electrochemical kinetics at electrode
4.1 Effect of potential on activation energy

2.3RT 2.3RT
 lg ic c   lg i0  lg ic
 nF  nF

0  re
lg i
lg i0
2.3RT 2.3RT
lg ia a   lg i0  lg ia
 nF  nF
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
4.2.1 Master equation
 nF 
ic  nFcOx (0, t )kc ,0 exp( )
RT
 nF 
ia  nFcRed (0, t )ka ,0 exp( )
RT
inet  ic  ia
 nF   nF 
 nFcOx (0, t )kc ,0 exp( )  nFcRed (0, t )ka ,0 exp( )
RT RT
  nF   nF  
 nFk0 cOx (0, t ) exp( )  cRed (0, t ) exp( )
 RT RT 

Master equation
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
Theoretical deduction of Nernst equation from Mater equation
  nF   nF  
inet  nFk0 cOx (0, t ) exp( )  cRed (0, t ) exp( )
 RT RT 
At equilibrium inet  0

cOx (0, t )  cOx

0
; cRed (0, t )  cRed
0

 nF   nF 
c exp(
0
Ox )c0
Red exp( )
RT RT
0 0
cOx nF RT cOx
0
 exp(  )   ln 0
cRed RT nF cRed
0
RT cOx
        ln 0 Nernst equation
nF cRed
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
Butler-Volmer equation
  nF   nF  
inet  nFk0 cOx (0, t ) exp( )  cRed (0, t ) exp( )
 RT RT 

  nF  nF 
i  i0 exp(  )  exp(  )
 RT RT 

Butler-Volmer equation
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
4.2.3 discussion of B-V equation
1) Limiting behavior at small overpotentials

 nF   nF
exp( )  1  i
RT RT

  nF    nF  
i  i0 1     1    
 RT   RT  

  nF    nF  
i 
nF
i  i0 1     1      i0 
 RT   RT   RT

Current is a linear function of overpotential

 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
nF
 RT Rct 
nF
Charge transfer resistance
  RTi0
i i0
False resistance
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
2) Limiting behavior at large overpotential

  nF  nF 
i  i0 exp(  )  exp(  )
 RT RT 

One term dominates

 nF
exp( )
RT  nF 
 exp     1% Error is less than 1%
 nF  RT 
exp( )   118 mV
RT

At cathodic polarization larger than 118 mV

inet  ic  ia  ic
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
 nF
i  i0 exp( )
RT
Taking logarithm of the equation gives:
 nF
lg i  lg i0  
2.3RT

2.3RT 2.3RT
 lg i0  lg i
 nF  nF
Making comparison with Tafel equation   a  b lg i

2.3RT 2.3RT
One can obtain a lg i0 b
 nF  nF
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
At 25 oC, when n = 1,  = 0.5
2.3RT
b
 nF b  118 mV The typical Tafel slope

lg i

118 mV 118 mV

lg i0

300 200 100 0 -100 -200 -300  / mV

 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization

Tafel plot:   log i plot

 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
4.2.4 determination of kinetic parameters
2.3RT 2.3RT
a lg i0 b
 nF  nF

For evolution of hydrogen over Hg electrode

  1.40  0.118lgi

  0.5
i0  1.6 1012 A  cm2

 nF
i0  nFcOx (0, t )kc ,0 exp( ) k  5 1013 cm  s1
RT
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
4.2.5 Exchange current density

1) The exchange currents of different electrodes differ a lot

Electrode solutions Electrode i0 / Acm-2

materials reaction

Hg 0.5 M sulfuric acid H++2e– = H2 510-13

Cu 1.0 M CuSO4 Cu2++2e– = Cu 210-5

Pt 0.1 M sulfuric acid H++2e– = H2 110-3

Hg 110-3 M Hg2(NO3)2 Hg22++2e– = 2Hg 510-1

+ 2.0M HClO4
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
2) Dependence of exchange currents on electrolyte concentration

Electrode reaction c (ZnSO4) i0 / Acm-2

1.0 80.0
0.1 27.6
Zn2++2e– = Zn
0.05 14.0
0.025 7.0

High electrolyte concentration is need for electrode to achieve

high exchange current.
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization

2.3RT ic When i0 is large and i << i0, c is small.

c  lg
 nF i0

 nF When i0 = , c=0, ideal nonpolarizable


i RTi0 electrode

2.3RT ic When i0 is small, c is large.

c  lg
 nF i0 When i0 = 0, c = , ideal polarizable
electrode
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
The common current density used for electrochemical study
ranges between 10-6 ~ 1 Acm-2.
If exchange current of the electrode i0 > 10~100 Acm-2, it is
difficult for the electrode to be polarized.
When i0 > 10-8 Acm-2, the electrode will always undergoes
sever polarization.

For electrode with high exchange current, passing current

will affect the equilibrium a little, therefore, the electrode
potential is stable, which is suitable for reference electrode.
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
 Chapter 4 Electrochemical kinetics at electrode
4.2 Electrochemical polarization
 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic
When we discuss situations in 4.2, we didn’t take diffusion
polarization into consideration

When diffusion take effect :

k BT G0.c  nF
ic  nFACOx (0, t )k exp( ) exp(  )
h RT RT
COx (0, t ) 0 kBT G0.c  nF
ic  nFA 0
COx k exp( ) exp(  )
COx h RT RT

COx (0, t )  nF
inet  ic  0
i0 exp( c )
COx RT
 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic
cOx (0, t )  nF
inet  ic  0
i0 exp( c )
cOx RT

At high cathodic polarization

i
c  c (1  )
s
i
0
i
id
i  nF
i  (1  )i0 exp( c )
id RT

i id  i  nF
( ) exp( c )
i0 id RT
 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic

i id  i  nF
( ) exp( c )
i0 id RT
i id  i  nF
Taking logarithm yields ln  ln( )( c )
i0 id RT

RT i RT id
Therefore: c  ln  ln
 nF io  nF id  i

Electrochemical term Diffusion term

At this time the total polarization comprises of tow terms:

electrochemical term and diffusion term.
 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic
RT i RT id
c  ln  ln
 nF i0  nF id  i
Discussion :
1. id >> i >> i0
No diffusion ec polarization
At small polarization : At large polarization:

i i

c 0 c
nF
i  i0  c 
RT
ln
i
RT  nF i0
 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic
RT i RT id
c  ln  ln
 nF i0  nF id  i
RT i
2. id  i << i0 c  ln 0 is invalid
 nF i
diffusion No ec
RT Id
d  ln( )
nF id  i
i  id
i


 log i
 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic

RT i RT id
c  ln  ln
 nF i0  nF id  i

3. id  i >> i0 both terms take effect

4. i << i0, id no polarization

 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic
When id >>i0
id diff

1 RT i RT id
id ec c  ln  ln
2
 nF i0  nF id  i
1/2 
1
id
RT 2 RT
0  1/ 2  ln  ln 2
 nF i0  nF
RT id RT RT
 ln  ln id  ln i0
 nF i0  nF  nF

 d1/ 2  RT
  
 d ln i0 id  nF
 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic

id diff RT i RT id
c  ln  ln
 nF i0  nF id  i
ec
RT Id
1/ 2  ln
 nF i0

 Chapter 4 Electrochemical kinetics at electrode
4.3 Diffusion on electrode kinetic

Tafel plot without diffusion polarization Tafel plot under diffusion polarization
i0 << i < 0.1 id electrochemical polarization
i between 0.1id  0.9id mixed control
i >0.9 id diffusion control
How to overcome mixed / diffusion control? The ways to elevate
limiting diffusion current