Lecture 9: Exchange Current Density Polarization Relationships

NPTEL Web Course

Lecture 9 Exchange Current Density Polarization Relationships

Keywords: Exchange Current, Tafel Relation, Concentration Profile.

A conceptual potential-current diagram depicting corrosion of zinc in an acid solution is given below (Fig. 9.1). Note that at the corrosion potential, E corr, there is a mixed equilibrium.

Fig. 9.1 Potential current diagram depicting acid corrosion of zinc

Considering a reversible hydrogen electrode, under equilibrium conditions, rate of oxidation (H2 2H+ + 2e) should equal the rate of reduction (2H+ + 2e = H2). Activation polarization (slowing down of the reaction) is a result of a slow step in the reaction. For example, for hydrogen evolution at cathode, the reactions involve several steps. (i) H+ + e = Hads (ii) Hads + Hads = H2 (iii)Then evolution of hydrogen molecules.
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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 9: Exchange Current Density Polarization Relationships

NPTEL Web Course

Any of the above steps can control the rate of the reaction and result in activation polarization.

Concept of exchange current density

When a metal in solution is at equilibrium, it implies rates of dissolution and deposition reactions are equal. When the above two reactions (anodic and cathodic) are in equilibrium, the rates (equal and opposite) of each of the two reactions are referred to as exchange current density. Expressing reaction rates in terms of current density, roxid = rred = based on Faradays law.

where roxid and rred are equilibrium oxidation and reduction rates. io is termed exchange current density which is the rate of oxidation and reduction at equilibrium. There is no net current under the above conditions even through the concept is a useful method of representing rates at equilibrium. ic = ia = io inet = ia ic = 0 A Kinetic expression for io is given as io = nFAKS ( (

Where KS is rate constant for the redox reaction = transfer coefficient A = Area

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 9: Exchange Current Density Polarization Relationships

NPTEL Web Course

Exchange current density (io) is dependent on a) Nature of the redox reaction b) Electrode composition / surface c) Concentration ratio of oxidized and reduced species d) Temperature.
Table 9.1 Approximate exchange current densities (io) for hydrogen reduction on various metals.

Metal Pb, Hg Zn Sn, Al Ni, Ag, Cu Fe, Au Pd, Rh Pt

Io(A/cm2) 10-13 10-11 10-10 10-7 10-6 10-4 10-2

For example, io for H+ / H2 reaction on platinum is about 10-2A/cm2 and for mercury it is about 10-13 A/cm2, which means it is easier to reduce hydrogen ions from acidic electrolyte on a platinum electrode unlike on mercury, which possesses a high Hydrogen-overvoltage. Exchange current densities are determined experimentally. The relationship between activation polarization (overpotential) and the rate of the reaction (ia and ic) is given below as Tafel relationship.

act =
For Anodic polarization act = For Cathodic polarization act = and are termed Tafel constants.

log

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 9: Exchange Current Density Polarization Relationships

NPTEL Web Course

Magnitude of io will indicate as to whether the redox reaction is reversible or irreversible. Lower io denotes higher overpotential, while higher io indicates lower overpotential (which means the reaction tends towards reversibility).

Concentration polarization
Concentration profile at a solid-solution interface is given in Fig. 9.2:

Fig. 9.2 Concentration distance profile at electorde solution interface

C0 = surface concentration of electroactive species. Cb = Bulk concentration. = diffusion layer thickness (thickness of the concentration gradient) E1 = E0 + ln Cb

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 9: Exchange Current Density Polarization Relationships

NPTEL Web Course

E2 = E0 + = E| - Erev = ln

ln C0

Ficks law of diffusion states = - AD Where = amount of species diffusing in unit time.

D = Diffusion coefficient = concentration gradient = = m (Cb C0)

=-A i = nF

(Cb C0)

iL (or id) = nFA (see Fig 9.3) iL = nFA Cb

(Cb C0)

(C0 0 when current reaches steady state)

Fig. 9.3 Depiction of limiting (diffusion) current

Eapp = E0 +

lan Cb
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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 9: Exchange Current Density Polarization Relationships

NPTEL Web Course

Where m = mass transfer rate constant .

= mcb
C0 = Cb

conc

= =

= ln

ln

Total =

act +

conc

red

=-

log

+ 2.3

log

Fig. 9.4 Combined cathodic polarization

Total cathodic polarization is the sum of activation and concentration polarization as shown in Fig. 9.4. Concentration polarization is generally absent in case of anodic polarization of metal dissolution.
a

log

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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore