ELECTROCHEMICAL KINETICS OF CORROSION

Reading Material: Chapter 3 in Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

Dr. Ramazan Kahraman

Chemical Engineering Department King Fahd University of Petroleum & Minerals Dhahran, Saudi Arabia
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Faradays Law
Charge is related to mass of material reacted in an electrochemical reaction: M Mn+ + neOne mol of metal n mols of electrons To produce one mol of metal ion and Reacts
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Faradays Law (Cont.)

One mole of metal (MW g) contains Avogadros number (61023) of metal atoms Hence each mole of metal will produce n times that many number of electrons Charge on the electron is 1.6 10-19 C (coulomb) Charge of one mol of electrons (61023 electrons) will then be 96500 C Hence one mole of metal will produce a charge of n 96500 C 96500 C/equivalent is known as Faradays constant (also in units of J/Vequivalent) Conversions: 1 A (ampere) = 1 C/s, 1 J = 1 CV
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Faradays Law (Cont.)

QM = I tM m= nF nF
where Q = charge (coulomb, C) I = current (amperes, A) (1 A =1 C/s) F = Faraday' s constant (96500 C/equivalent mol) n = number of equivalents (mols of electrons) transferred per mol of metal m = mass of metal oxidized (g) M = molecular (atomic) weight of metal (g/mole)

corrosion rate,
where

m = I t M / nF = i M r= nF tA tA
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A = surface area i = current density, I/A

How Fast will Corrosion Occur?

Corrosion kinetics Concerned with the rates of corrosion reactions Mixed potential theory: The corrosion potential will be that potential at which the sum of all anodic (positive) and cathodic (negative) currents on the electrode is zero (i.e. anodic current=cathodic current) (mixed equilibrium) (not an electrochemical equilibrium) Polarization The change in the potential of an electrode as current flows to or from it
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Corrosion of Zinc in Acid

When zinc is placed in acid the metal will start to dissolve (Zn Zn2+ + 2e-) and hydrogen will start to be liberated (2H+ + 2e- H2) according to the potential of the metal

Zn Zn+2
c a

e-

H+ H+

H2

Corrosion of Zinc in Acid

Electrochemical Potential Zn Zn2+ + 2eAt the Corrosion Potential, Ecorr, we have a stable mixed equilibrium

Ecorr 2H+ + 2e- H2 icorr Rate of Reaction Current density

Then the corrosion rate may be expressed as the corrosion current density, icorr

As the reaction involves transfer of charge, the rate of reaction may be expressed as a current per unit area, or current density

Corrosion of Zinc in Acid (Cont.)

Electrochemical Potential

Zn Zn2+ + 2e-

If the potential is above the Corrosion Potential, then it will fall due to production of electrons

2H+ + 2e- H2 Rate of Reaction Current density

If the potential is below the Corrosion Potential, then it will rise, due to consumption of electrons

Types of Polarization
Activation Polarization Concentration Polarization Resistance (IR-drop) Polarization

Activation Polarization
Result of a slow step in an electrode reaction at the anode or cathode For example, when hydrogen evolves at the cathode, the reaction might be considered as: Step 1: Step 2: Step 3: Hads H+ + eHads + Hads H2 Sufficient molecules of H2 combine and nucleate a hydrogen bubble.

Any one of these steps can control the rate of reaction and cause activation polarization.

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Activation Polarization (Cont.)

Example: Hydrogen reduction reaction under activation control.

[Corrosion Engineering, Mars Fontana, McGraw-Hill, 1986]

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Tafels Law for Activation Polarization

i E = Eo + b log io
where E= Eo = b= =

or

i = b log io

potential at current i potential at current io (ec for cathodic rxn and ea for anodic rxn) Tafel slope ((+) for anodic rxn, (-) for cathodic rxn) polarization (E-Eo at current i)

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Tafels Law at icorr

Anodic Polarization

Ecorr = ea + ba

icorr log io icorr log io

or

aat i

corr

= ba

icorr log io icorr log io

Cathodic Polarization

Ecorr = ec + bc

or

cat i

corr

= bc

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E-log i and Evans Diagrams

Plot E against log |i|, then activation polarization gives a straight line
Electrode Potential
Tafel slope expressed as mV per decade of current

mV log |i2 | - log |i1 | log |current|

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E-log i and Evans Diagrams (Cont.)

Eo and io for the cathodic reaction Anodic reaction, Tafel slope is positive

Electrode Potential

Mixed equilibrium occurs when sum of all currents is zero, i.e. at Ecorr and icorr for the corrosion reaction

log |current|
Eo and io for the anodic reaction Cathodic reaction, Tafel slope is negative
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Exchange Current Density, io

When a piece of metal is sitting in a solution at its equilibrium potential, this does not mean that the rates of the metal dissolution and reprecipitation reactions are zero. Instead it implies that the rates of the two reactions are equal. When the metal dissolution and reprecipitation reactions are in equilibrium, we refer to the (equal and opposite) rates (in terms of current density) of each of the two reactions as the exchange current density, io.
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Polarization

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Effect of Degree of Polarization

As degree of polarization gets higher (i.e. slope increases) icorr (corrosion rate) decreases.
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Example (Zinc in Acid)

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Example (Cont.)

Note that the reverse reactions, zinc deposition (Zn2++2e- Zn) and hydrogen oxidation (H2 2H++2e-), do not occur since the corrosion potential lies between 0.0 and -0.762 volt. Zinc deposition (Zn2++2e- Zn) can only occur at potentials more negative than -0.762 V, and hydrogen oxidation (H2 2H++2e-) only occurs at potentials more positive than 0.0 V.

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Concentration Polarization
Additional polarization (i.e. slowing down of a reaction) caused by depletion / drop in concentration of a reactant at the electrode surface or an excess of the unwanted species at the electrode surface (diffusion controlled polarization) Concentration polarization is low / insignificant until a limiting current density, iL, is approached (i.e. it becomes effective at high rates approaching iL) Limiting current density, iL, is the measure of a maximum reaction rate that cannot be exceeded because of a limited diffusion rate of a reactant
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Concentration Polarization (Cont.)

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

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Concentration Polarization (Cont.)

Example: Concentration polarization during hydrogen reduction.

[Corrosion Engineering, Mars Fontana, McGraw-Hill, 1986]

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Concentration Polarization (Cont.)

Effect of Solution Conditions on Concentration Polarization

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

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Concentration Polarization (Cont.)

conc

i 2.303RT = E Eo = log1 i nF L

Concentration polarization is usually negligible (insignificant) on anodes and usually ignored.

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Combined Polarization
Total Cathodic Polarization

c = act ,c + conc ,c
Anodic Polarization

ic ic 2.303RT log1 = bc log + i io nF L

a = act ,a

ia = ba log io
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Combined Polarization (Cont.)

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

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Combined Polarization (Cont.)

Oxygen reduction is often affected by concentration polarization
Electrode Potential
Rate of cathodic oxygen reduction without concentration polarization

Rate of cathodic oxygen reduction with concentration polarization Limiting current density - rate of reaction limited by availability of oxygen at the metal surface

log |current density|

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Combined Polarization (Cont.)

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

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Resistance Polarization
If there is a resistance between the anode and the cathode in a cell, then the current flowing through that resistance will cause a potential drop given by Ohms Law: V = IR This is important for paint films and for high resistance solutions

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Resistance Polarization
Resistance Polarization causes potential of anode and cathode to differ due to potential drop across solution, hence corrosion current is reduced

Electrode Potential

log |current density|

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Sample Polarization Curves

Iron in hydrochloric acid
Electrode Potential

Anodic iron dissolution Cathodic hydrogen evolution

log |current density|

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Sample Polarization Curves (Cont.)

Iron in aerated neutral NaCl solution
Electrode Potential

Anodic iron dissolution Cathodic oxygen reduction Cathodic hydrogen evolution

log |current density|

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Sample Polarization Curves (Cont.)

Iron in sulphuric acid (passivity to be studied later)

Electrode Potential

Oxygen evolution on passive film (or transpassive corrosion as metal is oxidised to a higher oxidation state) Anodic iron dissolution (with active-passive transition) Cathodic hydrogen evolution

log |current density|

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Effect of Oxidizer
Ecorr , icorr , rate of hydrogen evolution

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

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Effect of Exchange Current Density

[Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996]

The deriving force (difference between the half-cell reaction potentials is much larger for zinc than iron. However, the corrosion rate of zinc, icorr,Zn, is lower than that of iron, icorr,Fe, because of the low exchange current density for hydrogen reduction on zinc compared to iron and the comparatively low exchange current density for zinc dissolution.
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Effect of Dissolved Ion Concentration

Drawing appropriate polarization diagrams, determine the effect of increasing the concentration of dissolved H+ on Ecorr and icorr of a metal M corroding to dissolved M+ in a deaerated acid solution under activation control with all other parameters constant.

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Example Problem

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Home Work Problems

Prbs. 1, 6, 7 and 8 of Ch.3 in Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996.

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References

Principles and Prevention of Corrosion, Denny Jones, Prentice-Hall, 1996. Corrosion Engineering, Mars Fontana, McGraw-Hill, 1986. Corrosion and Corrosion Control, H. H. Uhlig and R. W. Revie, John Wiley & Sons, 1985. Web Site of Dr. R. A. (Bob) Cottis.

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