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Exercise

Corrosion kinetics
11 TH WEEK
Outline
❖ Introduction
❖ Polarization
❖ Corrosion rate from polarization data (Mixed
potential Theory)
❖ Passivity

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Introduction
Thermodynamics
❖ Equilibrium between metals and their environments
❖ Corrosion tendency of metals
❖ Qualitative picture of what can happen at a given pH and potential
(Pourbaix Diagram)
However:
❖ Considerations of equilibrium are irrelevant to the study of
corrosion rates
❖ Some metals with pronounced tendency to react (e.g., Al) react so
slowly that they meet the requirements of a structural metal
Kinetics of Corrosion
❖ Corrosion is thermodynamically possible for most
environmental conditions
❖ Kinetics is the study of the rates of corrosion Reactions
❖ Electrode kinetics are studied to predict the corrosion rates
for the actual conditions.
❖ An understanding of the fundamental laws of
electrochemical reaction kinetics is essential to develop
more corrosion-resistant alloys and techniques for corrosion
mitigation
What is Current i?
❖Unit: ampere (mA, μA, nA)
❖Electron flow is the result of a corrosion reaction
❖Current is a measure of the rate of the corrosion reaction
(electrons per second)
❖0 current is nothing! If i = 0 then no corrosion!
❖Anodic (oxidation) and cathodic (reduction) have different
polarity
❖Current (I) may be expressed as amps (A) , or current
density (i), A/cm2
Salt Solution Experiment
• U. R. Evans and Thomas Percy Hoar (a.k.a. T. P. Hoar
or Sam Hoar) (1907 – 1978)
• Experiment in 1932 using 3% KCl
• Corrosion was directly proportional to the current
Current Density and Faraday’s
Law
❑ Current density (A/cm2) was found to be
electrochemically equivalent to the weight loss of the
rusted section
❑ Current, I (amps), measured during a corrosion reaction
is the rate of charge transfer
❑ 1 Amp = 1 coulomb/s = 1 C/s
❑ Charge on an electron = 1.602 x 10-19 C
❑ Mole = 6.0235 x 1023 atoms (Avogadro’s number)
❑ Total charge on a mole of monovalent metal ions = 96369
C/mole → 1 Faraday
Faraday’s Law and Corrosion
Rates
• In the more general instance of anodic dissolution of a species
by charge transfer, nF coulombs, where n equals the number of
electrons involved in one act of the reaction, will be required for
1 mole of atoms
• Example: Fe → Fe2+ + 2e- n=2
• Corrosion rates can be expressed several ways
𝑖
𝑟= Moles/cm2.s
𝑛𝐹
M = atomic weight
𝑖𝑀
𝑟= g/cm2.s ρ = density
𝑛𝐹
𝑖𝑀
𝑟= cm/s
𝑛𝐹𝜌
Exchange Current Density
(ECD)
❖ Reduction and oxidation reaction occur at the same rate at the
equilibrium potential of a reaction
❖ For a Zn electrode, Zn ions are released from the metal and
discharged on the metal at the same rate
❖ Reaction rate in each direction can also be expressed by the
transport rate of electric charges, i.e., by exchange current density, io
❖ Net reaction rate and net current density are zero
Exchange Current Density
(ECD)
ECD is a measure of the reversibility of a reaction such as
2H+ + 2e- ⇌ H2
At the standard half-cell (redox E), E0H /H2 , of this reaction is in
equilibrium where the forward rate (left to right), rf, is equal to the
reverse rate (right to left), rr
𝑖𝑜 𝑀
𝑟𝑓 = 𝑟𝑟 =
𝑛𝐹

where i0 = ECD,
Note:
ECD is affected by the nature of the surface
E is not affected by the nature of the surface
Exchange Current Density
Polarization and Overvoltage
❖ When two such as those illustrated for zinc in air-free
hydrochloric acid, or for zinc in aerated hydrochloric
acid occur over a single metallic surface, the corrosion
potential that results from this situation is a compromise
between the various equilibrium potentials of all the
anodic and cathodic reactions involved.
❖ The difference between the resultant potential (E) and
each individual reaction equilibrium potential (Eeq) is
called polarization and quantified in terms of an
overpotential (η) as in equation:

𝜂 = 𝐸 − 𝐸𝑒𝑞
Polarization and Overpotential
Anodic polarization → when the anodic processes on the electrode are
accelerated by changing the specimen potential in the positive (noble)
direction.
Cathodic polarization→ when the cathodic processes are accelerated by
moving the potential in the negative (active) direction.
There are three distinct types of polarization and these are additive, as
expressed in equation:

𝜂𝑡𝑜𝑡𝑎𝑙 = 𝜂𝑎 + 𝜂𝑐 + 𝐼𝑅

• ha is the activation overpotential


• hc is the concentration overpotential,
• IR is the ohmic drop.
Polarization and Overvoltage
Consider the standard Zn/H2 electrochemical cell shown in Figure
The potentials of the two electrodes
are not at the values from Table
Standard reduction potential because
the system is now a non-equilibrium
state.
The displacement of each electrode
potential from its equilibrium value is
termed polarization, and the
magnitude of this displacement is the
overvoltage (η).

𝜂 = 𝐸 − 𝐸𝑒𝑞

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Polarization and Overvoltage
❖ Overvoltage is expressed in terms of plus or minus volts (or
millivolts) relative to the equilibrium potential.
❖ Example, suppose that the zinc electrode in Figure 17.5 has a
potential of -0.621 V after it has been connected to the
platinum electrode. The equilibrium potential is -0.763 V (Table
standard reduction potential), and, therefore,
𝜂 = −0.621 − −0.763 = +0.142 𝑉
❖ Polarization can be conveniently divided into two different
types:
(i) Activation polarization
(ii) Concentration polarization
Activation
polarization
For the case of Zn, the step of reaction:
1. Adsorption of H ions from the
solution onto the zinc surface
2. Electron transfer from the zinc to
form a hydrogen atom, H+ + e- → H
3. Combining of two hydrogen atoms
to form a molecule of hydrogen, 2H
→ H2
4. The coalescence of many hydrogen
molecules to form a bubble
Activation polarization refers to the condition in which the reaction rate is
controlled by the one step in the series that occurs at the slowest rate.
The term activation is because an activation energy barrier is associated
with this slowest, rate limiting step.
Activation polarization
Julius Tafel (Swiss) mathematically
described the relationship between
𝜂𝑎 and i in 1905
Anodic branch
𝑖
𝜂𝑎 = ±𝛽 𝑙𝑜𝑔
𝑖𝑜
Tafel Slope
Where: β and i0 are constants for the
particular half-cell. i0 is exchange
current density.
For a hydrogen electrode, plot of
cathodic branch
activation polarization overvoltage
versus logarithm of current density for
both oxidation and reduction
reactions.
Detail of Evans Diagram Near
ECD
Concentration Polarization
Concentration polarization exists when the reaction rate is limited by diffusion
in the solution.
For example, consider again the hydrogen evolution reduction reaction.

Concentration polarization
Concentration Polarization
❖Concentration polarization data
can be plotted as overvoltage
versus the logarithm of current
density.
❖It may be noted from this figure
that overvoltage is independent
of current density until i
approaches iL; at this point, 𝜂𝑐
decreases abruptly in magnitude.

2.3 𝑅 𝑇 𝑖
𝜂𝑐 = log 1 −
𝑛𝐹 𝑖𝐿
Activation and Concentration
polarization
❖ Both concentration and
activation polarization
are possible for How difficult
reduction reactions. the reaction?

❖ Under these
circumstances, the total How much
overvoltage is the sum the reactant
of both overvoltage at the
contributions. surface?

𝜂𝑡𝑜𝑡𝑎𝑙 = 𝜂𝑎 + 𝜂𝑐
Polarization
❖ Activation polarization is usually the controlling factor during
corrosion in strong acids.
❖ Concentration polarization usually predominates when the
concentration of the active species is low;
❖ for example, in dilute acids or in aerated waters where the active component,
dissolved oxygen, is only present at very low levels.

❖ The ohmic drop is usually when studying corrosion phenomena


with a clear separation of the anodic and cathodic corrosion sites,
e.g. crevice corrosion.
❖ The ohmic drop → important variable in anodic and cathodic
protection.
Polarization
❖ Knowing the kind of polarization which is occurring can be
very helpful, since it allows an assessment of the
determining characteristics of a corroding system.
❖ For example, if corrosion is controlled by concentration
polarization, then any change that increases the diffusion
rate of the active species (e.g., oxygen) will also increase
the corrosion rate. For example by agitating or stirring.
❖ However, if a corrosion reaction is activation controlled
then stirring or agitation will have no effect on the
corrosion rate.
End
Determination of Corrosion
Rates
Corrosion rates can be measured by applying a potential
to produce a polarization curve (the degree of potential
change as a function of the amount of potential applied)
for the metal surface

When the potential of the metal surface is polarized by


the application of the potential in a positive direction, it
is said to be anodically polarized; a negative direction
signifies that it is cathodically polarized
Determination of Corrosion
Rates
❖ Degree of polarization is a measure of how the rates of the
anodic and the cathodic reactions are affected by:
❖ Surface processes (adsorption, film formation, ease of
release of electrons, etc.) factors - activation polarization
❖ Concentration of metal ions, dissolved oxygen, etc. in
solution - concentration polarization

❖ Variation of i as a function of E (polarization curves/Evans


diagrams) allows the evaluation of the effect of concentration
and activation processes on the rate of corrosion
Corrosion Rates from
Polarization Data
▪ Concept of polarization is useful
to the determination of corrosion
rates.
▪ Upon immersion, both hydrogen
and zinc experience activation
polarization along their respective
lines.
▪ Oxidation and reduction rates are
equal, at the intersection of the
two line segments;
▪ The intersection is the point of
0
corrosion potential (ECorr) and the 𝐸𝐻2 =0𝑉
corrosion current density (iCorr).
0
𝐸𝑍𝑛 = −0.763 𝑉
▪ Ecorr = mixed potential
Mixed Potential Theory
Mixed Potential Theory
Mixed Potential Theory
Mixed Potential Theory
Mixed
𝐸𝐻0 + ,𝐻2
Potential
Theory
The corrosion rate 𝑖𝑐𝑜𝑟𝑟
can be calculated
as
𝐸𝑐𝑜𝑟𝑟

𝑖𝑐𝑜𝑟𝑟
𝑟= 0
𝐸𝑍𝑛,𝑍𝑛
𝑛𝐹 2+
Example
Zinc experiences corrosion in an acid solution according to the reaction

The rates of both oxidation and reduction half-reactions are controlled


by activation polarization.
(a) Compute the rate of oxidation of Zn (in mol/cm2-s), given the
following activation polarization data:
For Zn For Hydrogen
0
𝐸𝑍𝑛,𝑍𝑛 2+ = -0.763 V 𝐸𝐻0 + ,𝐻2 = 0 V
i0 = 10-7 A/cm2 i0 = 10-10 A/cm2
β = 0.09 β = -0.08
(b) Compute the value of the corrosion potential.
Example: A533 Gr. B in Boric
Acid
PASSIVITY
▪ The passivation of a metal as it pertains to corrosion refers to the
formation of a protective surface layer of reaction product that inhibits
further reaction;
▪ In other words, the passivation of metals refers to their loss of chemical
reactivity in the presence of a particular environmental conditions;
▪ There are two (2) main theories regarding the nature of the passive
film:
a) The oxide-film theory- it is believed that the passive film is always a
diffusion-barrier layer of reaction products (e.g., metal oxides or other
compounds) that are separated the metal from its environment and slow
down the reaction rate;
b) The adsorption theory- it is believed that passive metals are covered by
chemisorbed films of oxygen; such a layer is supposed to displaced the
normally adsorbed H₂O molecules and slow down the rate of anodic
dissolution involving the hydration of metals ions;

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Passivity
Active region - the behavior of this
material is identical to that of a normal
metal.
Passive region - if more oxidizing agent is
added, the corrosion rate shows a sudden
decrease, further increases in oxidizing
agents produce little, if any, change in the
corrosion rate of the material.
Transpassive region - at very high
concentrations of oxidizers or in the
This passivation phenomenon may be presence of very powerful oxidizers the
explained in terms of polarization corrosion rate again increase with
potential–log current density curves increasing oxidizer power.

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