Electrochemical corrosion

Corrosion of metals by acids. (H2 evolution type)

Standard Gibbs free energy of
Recall the electrochemical reaction
When activities of oxidized and
reduced species are all unity
Standard electrode potential for half cell reaction

• Can be represented as reduction potential for M+ + e−  M (if denoted as EM°)

For the same rxn)
• Can be represented as oxidation potential for M M+ + e− (then it is −EM°)
Higher is E° (i.e., lower the ) greater is the propensity for the
electrochemical reaction.
• Dissolution potential (oxidation potential in case M is metal)
Higher the dissolution potential greater the propensity of the metal to oxidize.
• Discharge potential (reduction potential in case M is metal or H)

Observed H2 discharge potential depends upon the type of the

electrode
 The additional potential (beyond the thermodynamic requirement) needed
to drive a reaction at a certain rate is called the overpotential η.

• Hydrogen overvoltage (w): difference between the observed potential at

which H2 evolves and the theoretical reversible value (obtained from
Nernst eqn.)
Hydrogen reduction potential (𝑤 = −𝜂)

By convention E°H at Pt electrode in acid solution is zero (w=0).

Consider reactions: Potential E° (V) w (in V)

≈−0.12 ≈ 0.6 (at Pb electrode)
≈−0.75 ≈ 0.7 (at Zn electrode)
(At Pt electrode, in acid
≈ 0.0 (at Pt electrode)
solution, by convention)
(In neutral solution) ≈−0.4

Pb should displace H2 from acid solution. Zn should displace H2 from neutral

solution (as can be concluded from 𝐸 ∘ )
 Fact is:

•Pb doesn’t displace H2 from acid solution. Zn doesn’t displace H2 from

neutral solution but dissolves slowly in acid solution.

Explained by H2 overvoltage at Pb and Zn electrodes

Discharge (reduction) potential of H2

At Pb electrode in acid solution ≈ EH° − w ≈ − 0.6 V

At Zn electrode in neutral solution ≈ EH° − w ≈ − 0.4 − 0.7 = − 1.1 V

Dissolution (oxidation) potential of H2

At Pb electrode in acid solution ≈ 0.6 V > 0.12 V (dissolution pot. of Pb)

At Zn electrode in neutral solution ≈ 1.1 V > 0.75 V (dissolution pot. of Pb)

No H2 evolution takes place

 Zn dissolves in acid solution slowly because:

EH° − w ≈ − 0.0 − 0.7 = − 0.7 V (close to reduction potential of Zn ≈ − 0.75 V)

Dissolution (oxidation) potential of H2 at Zn = 0.7 V < 0.75 V (dissolution

pot. Of Zn)
Hence Zn dissolves

Zn – Cu couple in acid solution (poss. rxns.: Zn Zn2+, Cu  Cu2+, 2H+ H2 (at Cu or Zn),
since initial species are Zn, Cu & H+, assuming no cations initially )

0.75 V > - 0.2 > - 0.34 > -0.7

Zn dissolves more rapidly here due to

EH° − w (at Zn electrode) ≈ − 0.7 V development of short circuited cell!
EH° − w (at Cu electrode) ≈ − 0.2 V
Metal (like Zn) corrodes more faster

− in contact with more nobler metal (like Pt or Cu) having low H2 overvoltage
− and in solution with higher H+ ion concentration.

• Pinch of copper sulfate to an acid solution expedites Zn disolution as Cu

deposits on various parts of Zn and large number of local short circuited
cells are set up.
0.75 V > + 0.34 > - 0.2 > -0.7

Prevention:
• impress a more negative EMF from a external source than the total emf of
the short circuited cell in the metal couple
• If the overvoltage of the noble metal is large. For e.g. mercury Hg, then
attack on less noble metal in the metal couple is hindered. So Zn in
amalgamated.
Conditions (requirements) for corrossion of metals by acid:

• Metal in a solution having high H+ ion concentration.

• Combination of 2 metals with difference in hydrogen over voltage.

 Corrosion by oxygen (Differential aeration effect)

Reactions in the cathodic regions of the metal:

or neutral solution
Reaction at anodic regions of metal:
• Corrosion current for Zn is larger than that for Fe, which is larger than that for Cu
as EZn > EFe > ECu (order of oxidation potentials).
• When metal is Fe, the corrosion phenomena is commonly called rusting.
Iron sheet
Water line
Oxygen defect corrosion in Fe or
rusting occurs where there is no
O2
supply of O2
4 OH- Requirement: Difference in
4 e− 2 H20 O2 conc. on the metal.
Fe(OH)2

2 Fe2+ • Oxygen acts as a depolarizer by

Aq. soln 2 Fe
accepting electrons.
 Rusting of iron is where metallic iron is converted into various oxides or
hydroxides when exposed to moist air.

Sequence of steps are approximately as follows:

The deposition of solid rust is even more complicated, with such sub-steps
as the formation of hydroxide via intermediate stepwise hydrolysis, followed
by formation of polybases first dissolved, then colloidal, then solid, followed
by partial dehydration of the hydroxide. Also, while the orthorhombic
goethite, α-FeOOH, usually is a main constituent of rust, there also are
varying amounts of orthorombic lepidokrokite, γ-FeOOH, rhomboedric
hematite, α -Fe2O3, and tetragonal maghemite, γ -Fe2O3. In rust, iron
predominantly is trivalent, but from thermodynamics a lower valence state
is expected at the rust/iron interface, that is, cubic magnetite, Fe3O4.
 When hydrated ferrite/ferrate, hydroxides are ignored
• The equilibrium
potentials of the H2 and
Metal electrode the O2 electrode as
potential in function of pH have been
corrossion, the shown
anodic potential • Differences between EO2 & EH2
and the equilibrium potentials
for metal dissolution or
oxide/hydroxide formation
measure the thermodynamic
driving force for acid and for
oxygen corrosion. Implying for
O2 corrosion
(or etc.) <ε<
EO2.

• iron dissolution to complex

ferrite and/or ferrate ions in
solutions of higher pH are
ignored.

Ref: Corrosion of Metals: Physicochemical Principles and Current Problems, by Kaesche,

Helmut (2003) . Free e-book preview
http://www.springer.com/materials/special+types/book/978-3-540-00626-8
When hydroxides and hydrated forms of iron are neglected electrode reactions (anodic)
are (from figure in last slide):
• In acidic, neutral and slightly basic solution

(discussed earlier)
• Further rxns. when Fe2+ is present and as pH is increased are

(Region 2)

(Region 3) In neutral & basic

solution
(Region 4)

(Region 5)

(Region 6) In acidic
solution
(Region 7)

In aerated solution, or in presence of moisture:

Oxides are formed by electrode
2Fe2+ + H2O+ 1/2O2 ⟶ 2Fe3+ + 2OH− rxn. as in region 7.
Generally oxides are formed in weakly acid, neutral & basic solutions. Oxides are also
formed in acidic solution via the formation of Fe3+
 With the hydrated forms & hydroxides included the potential-pH diagrams
becomes complicated. Few conclusions are:

It is proposed formation of magnetite goes via the formation of Fe(OH)2 (at

temperatures below 85°C (perhaps ∓ 20°C )as:

(cr) crystalline
condition in iron-
water system

Ref. Beverskog, B. and Puigdomenech, 1.: Corr. Sci. 38 (1996) 2121

 Corrosion by metal contact; corrosion inhibition
• The contact of dissimilar metals commonly results in corrosion.

For example: Fe in contact with Cu immersed in a conducting solution that does

not contain appreciable amounts of either Fe2+ or Cu2+, Fe acts as anode and Cu
as cathode (oxidation potential of Fe is higher than Cu).

At anode: Fe ⟶ Fe2+ + 2e−

At cathode: Hydrogen evolution or oxygen reduction (depending

upon the solution)

The result is a rapid corrosion of the less noble metal, iron.

If the two metals were not connected, both would corrode in an oxygenated
solution; but if the two metals are electrically connected, only the more
active metal corrodes.

This forms the basis of corrosion protection by sacrificial anode. A bar of Zn or

Mg is electrically connected to steel that is to be protected. (Zn or Mg corrodes).
•Exercise: Write half cell reactions for the sacrificial anode and also for cathode.
 … corrosion inhibition

• In some instances the metal to be protected is connected to an external

source of power; a sufficiently cathodic potential is impressed to reduce the
corrosion current to zero.

• Coatings are used to reduce corrosion. E.g. tin plate. To be effective it must
be impermeable or capable of resealing itself if it is perforated. The protective
oxide on aluminum reseals itself in air if it is broken.

• Anodic inhibitors: e.g alkalis, and oxidizing agents inhibit corrosion by

assisting the formation of a relatively adherent film of oxide on the metal and
assisting the repair of breaks in the coating.

• Cathodic inhibitors: Some may poison the H2 evolution at cathode, thus

increasing the hydrogen overvoltage and reducing the corrosion current.
Others, for e.g. Cu2+, may simply block the O2 access to cathode by forming a
film and thus shut off the corrosion current.
 Depolarizer

Hydrogen depolarizer is a substance that react with H2 (or react itself) to permit a
process to occur at cathode at much lower (negative) potential. E.g. O2, O2 from
air or any oxidizing agent.

Recall oxygen acts as a depolarizer by accepting electrons in case

of rusting, there is no evolution of H2.

• The term depolarizer is also frequently used to denote a substance that is

preferentially oxidized or reduced, to prevent an undesirable electrode reaction.
… depolarizer

Electrochemical corrosion of iron

Corrosion often begins at a location
(1) where the metal is under stress
(at a bend or weld) or is isolated
from the air (where two pieces of
metal are joined or under a loosely-
adhering paint film.) The metal ions
dissolve in the moisture film and
the electrons migrate to another
location (2) where they are taken
2 +
up by a depolarizer. Oxygen is the
most common depolarizer; the
resulting hydroxide ions react with
the Fe2+ to form the mixture of
hydrous iron oxides known as rust.
 Corrosion by depolarizer

Unless special precautions are taken to exclude air, a depolarizer (O2 in air)
is always present, and if this is freely available the conditions of metallic
corrosion are changed.

Since there is now no actual evolution of hydrogen gas at the cathodic

regions, the overvoltage of the noble constituent of the system is
unimportant.

• For a metal composite baser of the metal is attacked irrespective of the

hydrogen overvoltage (since no H2 evolution).

• Fe in imperfect `tin plate’ is readily corroded in air provided moisture is

present, but in absence of O2 the high overvoltage of Sn prevents any attack
of Fe.
Fe is
baser
 For imperfect tin plate on Fe:

− In presence of O2 (i.e moisture), corrosion is as discussed in rusting.

− In absence of O2, dissolution (oxidation) potential of H2

i) (in acid solution) ≈ 0.53 > 0.44 (oxidation pot. of Fe) Hence Fe
doesn’t
ii) (in neutral solution) ≈ 0.93 V > 0.44 (oxidation pot. of Fe) corrode

greater oxidizing
potential
• In uniform piece of metal any portion which is strained is less noble than
unstrained ones. These differences permits local voltaic cells to set up in the
presence of depolarizer. Corrosion of baser regions occur.

• In citric acid and oxalic acid solutions it is Sn, rather than Fe, that is
attacked, because Sn forms complex anions in these particular electrolytes
with the result that its dissolution potential exceeds that of Fe in same
solutions.