Introduction to electrochemistry

Kinetics of aqueous corrosion

• Activation polarisation
– Tafel equations and Evans diagram
– Mixed potential theory

Maurice Monjerezi
Charge transfer rate and current density
– In an electrochemical cell, the rate of oxidation at the anode
M → Mn+ + ne-, may be related to the cell current, I

 dN 
⇒ I = nF  −  Recall: Faraday’s
 dt 

It is more common in electrochemistry to consider current density, i or j:

I nF  dN 
j= = − 
A A  dt 

– The current (or current density) is related to the rate of loss of

metal
Activation Polarization

When chemical reaction is the slowest step in the corrosion

mechanism (i.e. there are no diffusional mass transport limitations):

• Overcoming the activation energy of the reaction is the

significant step

• We say that the process is controlled by “activation polarisation"

 Bultler-Volmer

αnF αnF
η ⇒ ln j = ln jo + η Anodic current
j = jo e RT
RT
RT j RT
⇒ ηa = ln ηa = β a log
j where β a = 2.303
αnF jo
Or
jo α nF
Tafel equations

− (1− α)nF
η (1 − α)nF
j = jo e RT ⇒ ln j = lnjo − η Cathodic current
RT
RT j RT
⇒ ηc = − ln Or η = β log j whereβ c = −2.303
(1 - α )nF jo c c
j o
(1 − α ) nF
4
 Evans Diagram
 j
η a = β a log  β a = 2.303 RT  j β c = −2.303
RT
 jo  α nF η c = β c log  (1 − α ) nF
 jo 
η (V)

slope = β a

η =0 Deviation from linearity at low

η as the reverse reaction can
no longer be ignored

slope = β c

log10 jo log10 j
• Such a plot of potential against (log current) is called the Evans diagram.
It is useful as it combines thermodynamics information (potential) and
kinetic information (current density) on the same plot

• Note that such a plot enables exchange current density jo to be obtained

experimentally

• We are normally interested only in the behaviour when polarization is

moderately large (i.e. the Tafel equation region). We can use the Tafel equation
to predict the new current density if there is a change in metal potential e.g. if it
is connected to an external source of current (such as a potentiostat, or DC
battery), or another electrode.

• WARNING: literature often takes βc to be positive. Literature also often

differentiates between “anodic polarization”, ηa which applies when our η > 0,
and “cathodic polarisation”, ηc which applies when our η < 0
 Mixed Potential Theory

• All electrochemical corrosion processes are composed of one or more

anodic reactions and one or more cathodic reactions.

• This situation can occur even on a single metal surface (due to

differences in microstructure); alternatively, it can apply when there are
two different metals present.

• The difference in potential between the anode and cathode will cause a
flow of electrons. This will reduce the potential of the cathode, and
increase that of the anode.

Charge conservation
• The electron released at the anodes must equal
the electron consumption at the cathodes.
 Mixed Potential Theory
Charge conservation

Single reaction
with back A a ja = I cell = Ac jc
reaction

Same areas e.g.

same metal A a = Ac ⇒ j a = jc
surface

• The potential at which charge conservation is obeyed (in the absence of any
external source of current) is termed either the "mixed corrosion potential" (as it
is in between that of the anode alone and that of the cathode alone), or the
"free corrosion potential". We shall give it the symbol Ecorr.

The situation can be shown schematically on an Evans diagram

An Evans diagram for a single metal surface (which guarantees Aa = Ac)

Eo, c ; jo, c
E (V)

Cathodic
slope = β c

Ecorr ; jcorr
anodic

Eo, a slope = β a

jo, a log10 j
E.g. iron in acidic environment (Aa = Ac)
NOTE:
• The value of Eo, a is the standard electrode potential for the
anodic reaction, adjusted by the Nernst equation as appropriate.
Similarly for Eo, c

• The intersection point predicts jcorr, the current density, and thus
the rates of the anodic and cathodic reactions can be obtained.

• If the electrodes are separate, then

– The relative areas of the cathode and anode will need to be
taken into account
– The resistance of the solution may be significant: in that case
there will be a potential drop through the solution equal to IR
 Example: Does Fe or Zn corrode faster in a de-aerated hydrochloric acid?

Data:
Fe2+ + 2e- → Fe Eo = -0.44 V jo = 10-6 A/m2
Zn2+ + 2e- → Zn Eo = - 0.76 V jo = 10-7 A/m2

2H+ + 2e- → H2 Eo = 0.00 V jo = 10-6 A/m2 for Fe

jo = 10-10 A/m2 for Zn
Take βa = 0.1 V and βc = -0.1 V for both cases (a typical value). Assume
equal areas of electrode and negligible solution resistance.
An Evans diagram ( Aa = Ac)

0 ;-10 0; -6
E (V)

Cathodic
Ecorr (Fe) ; jcorr (Fe)

Ecorr (Zn) ; jcorr (Zn)

-0.44 V anodic

-0.76 V

-7 log10 j
 Example: Does Fe or Zn corrode faster in a de-aerated hydrochloric acid?

For Zn:
Ecorr ( Zn ) + 0.76 Ecorr ( Zn ) − 0.00
0.1 = − 0.1 =
jcorr ( Zn ) jcorr ( Zn )
log log
10 −7 10 −10

Rearrangement
gives: E = −0.53V jcorr ( Zn ) = 2 x10 −5 A/m 2
corr ( Zn )

For Fe:
Similar calculation for iron gives

Ecorr ( Fe ) = −0.22V jcorr ( Fe ) = 1.6 x10 −4 A/m 2

• Hence iron dissolves FASTER than zinc in acid despite the smaller
thermodynamic driving force.
Example 2
Lead experiences corrosion in an acidic solution according to the reaction
Pb + 2H+ → Pb2+ + H2
Assuming that the rates of both oxidation and reduction half reactions are
controlled by activation polarization, calculate the corrosion potential Ecorr and
the rate of oxidation of lead (in mol/cm2 s) using the data below:

Data:
For lead (Pb|Pb2+): For hydrogen (H2|2H+):
Eo = -0.126 V Eo = 0.0 V
jo = 2 x 10-9 A/cm2 jo = 1 x 10-8 A/cm2
β = + 0.12 V β = - 0.10 V
 Summary
• In general we can use Evans diagrams and the Tafel equation to predict
corrosion rates based on the electrode reactions likely to occur in the system.

• It can be seen that the rate of corrosion depends on:

– the electrode potentials of the reactions involved
– the exchange current densities (which depend on surface chemistry)
– the Tafel parameters
– any external applied potential

• Note that the charge conservation condition, Aaja = Acjc, implies corrosion will be
particularly rapid if Ac >> Aa. A general principle in corrosion prevention is to
avoid the situation of a large cathode and small anode area.

• However, there are two additional factors that affect corrosion rate that we
have not yet considered: diffusional limitations and passivation .