CHAPTER 2

CORROSION PRINCIPLES

Chapter Outlines

2.1 Oxidation and Reduction Reactions

2.2 Standard Electrode Half- Cell Potentials
2.3 Standard EMF Series
2.4 Galvanic Cells With 1 Molar Electrolytes
2.5 Galvanic Cells Not 1Molar Electrolytes
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 2.1 Oxidation and Reduction Reactions

 In metal, corrosion process is normally

electrochemical @ electrochemistry
(a chemical reaction in which there is transfer
of electrons from one chemical species to
another)

 2 reactions that occur during corrosion process:

i. Oxidation reaction
ii. Reduction reaction

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i. Oxidation reaction @ anodic reaction

 Definition:
the removal of one or more electrons from an
atom, ion or molecule
 Equation:
M Mn+ + ne-

(in which M becomes an n+ positively charged ion and in the

process loses its n valence electrons; e- is used to symbolize
an electron)

 Example: Zn  Zn2  2e

 Anode is the side at which oxidation takes place.

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ii. Reduction reaction

 Definition:
the addition of one or more electrons to an atom, ion or
molecule (because the electrons generated from each metal
atom that is oxidized must be transferred to and become a part
of another chemical species = reduction reaction)

 Equation:
M+ + e- M(n-1)+
(some metals undergo corrosion in acid solutions, which have a high
concentration of hydrogen (H+) and hydrogen gas (H2) is evolved)

 Cathode is the side at which reduction occurs

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 There are 3 possibilities of reaction that can occur at
cathode (reduction):

 First possibilities

Cathodic half- cell reaction : 2H  2e  H2 (gas )

Condition : if the electrolyte is an acid
solution
Reaction : hydrogen ions in the acid solution
will be reduced to hydrogen atom to
form diatomic hydrogen gas

 Second possibilities
 
Cathodic half- cell reaction : O2  4H  4e  2H2O
Condition : if the electrolyte also contain
oxidizing agent
Reaction : oxygen will combine with hydrogen
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 Third possibilities

 
Cathodic half- cell reaction : 2O  2H2 O  4e  4(OH)
Condition : if the electrolyte is basic or
neutral and oxygen is
present
Reaction : oxygen and water molecules
will react to form hydroxyl
ions

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 iii. Overall Electrochemical Reaction

 Consist of at least one oxidation (half reaction) and

one reduction (half reaction), and will be the sum of
them
 Example:
(Zinc metal immersed in an acid solution)

At some regions on the metal

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oxidation or corrosion
 Oxidation half reaction:

Zn  Zn2  2e
Since Zn is a metal and good electrical conductor, these electrons
may be transferred to an adjacent region at which the H+ ions are
reduced.
 Reduction half reaction:

2H  2e  H2 (gas )

 Total electrochemical reaction:

Zn  Zn2  2e
2H  2e  H2 (gas )

4/11/2019 Zn + 2H+Asyadi Zn2+ + H2 (gas) 8

 Zinc metal
Chemical reaction:
Zn + 2HCl ZnCl2 + H2

Ionic form:
Zn + 2H+ Zn2+ + H2

Half- cell reaction:

Zn Zn2+ + 2e- (oxidation)
2H+ + 2e- H2 (reduction)

hydrochloric acid

Fig. Reaction of hydrochloric acid with zinc to produce hydrogen gas

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 2.2 Standard Electrode Half- Cell Potentials

 Every metal has a different tendency to corrode in a

particular environment

 E.g. ‘zinc is chemically attacked or corroded by dilute

hydrochloric acid, whereas gold is not’

 Method for comparing the tendency for metals to form

ions in aqueous solution is to compare their half- cell
oxidation or reduction potentials (voltages) to a
standard hydrogen- hydrogen ion half- cell potential.

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 Experimental Setup for the Determination of
Half- cell Standard Electrode Potentials

Experimental setup for the determination of the standard emf of zinc. In a beaker a
Zn Electrode is placed in a solution of 1 M Zn2+ ions. In the other there is a
standard hydrogen reference electrode
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11
immersed in a solution of 1 MH+ ions which contains H2 gas at 1 atm.
Standard Hydrogen Electrode

 Represent only differences in electrical potential and thus it is

convenient to establish a reference point/ reference cell to which
other cell halves may be compared.

 It consist of an inert platinum electrode in a 1M solution of

H+ ions, saturated with hydrogen gas that is bubbled through
the solution at a pressure of 1 atm and temperature of 25°C.

 The platinum itself does not take part in the electrochemical

reaction: it acts only as a surface on which hydrogen atoms
may be oxidized or hydrogen ions may be reduced.

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 2.2 Standard EMF Series

 Electromotive force (EMF) series:

is generated by coupling to the standard
hydrogen electrode, std half- cells for
various metals and ranking them according to
measured voltage.

 Table 17.1- show the list of the standard half-

cell potentials of some selected metals which
represents the corrosion tendencies for the
several metals
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Increasingly inert
(cathodic)

Increasingly active
(anodic)

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 those metals at the top (Au & Pt) --- are noble or
chemically inert

 Moving down --- metals become increasingly more

active (more susceptible to oxidation) (sodium &
potassium)

 The voltages --- are for the half- reactions

oxidation reaction: electron on the right hand side

M1 Mn+ + ne- V1º

reduction reaction: electron on the left hand side

(sign of the voltage changed)

M+ + e- M(n-1)+ V2º
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 Overall cell potential ΔV° is:

ΔVcell° = V° 1 + V° 2

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 GALVANIC CELLS

Galvanic couple:
Two metals electrically connected in a liquid
electrolyte wherein one metal becomes anode and
corrodes, while the other acts as a cathode

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 2.4 Galvanic Cells With 1 Molar Electrolytes

 Can be constructed with two dissimilar metal electrodes each

immersed in a 1M solution of their own ions

 The two solutions are separated by a porous wall to prevent

their mechanical mixing, and an external wire in series with a
switch and a voltmeter connects the two electrodes

 E.g.:
zinc electrode immersed in a 1 M solution of Zn2+ ions and
another of copper immersed in a 1 M solution of Cu2+ ions with
the solutions at 25°C

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A macroscopic galvanic cell with zinc and copper electrodes. When the switch is closed
and the electrons flow, the voltage difference between the zinc and copper electrodes
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is -1.10V. The zinc electrode is the anode of the cell and corrodes.
 Calculation of electrochemical potential of Zn- Cu galvanic cell

 From the Standard emf Series:

Zn Zn2+ + 2e- E° = -0.763 V
Cu Cu2+ + 2e- E° = +0.340 V

 Oxidation half- cell reaction: (ANODE)

Zn Zn2+ + 2e- E° = -0.763 V°1

 Reduction half- cell reaction: (CATHODE)

Cu2+ + 2e- Cu E° = -0.340 V°2

 Overall reaction (by adding):

Zn + Cu2+ Zn2+ + Cu E°cell = V°1 + V°2

= -0.763 + (-0.340)
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Problem 1:

A galvanic cell consist of an electrode of zinc in a 1M ZnSO4

solution and another of nickel in a 1 M NiSO4 solution. The two
electrodes are separated by a porous wall so that mixing of the
solutions is prevented. An external wire with a switch connects the
two electrodes. When the switch is just closed:

(a) At which electrode does oxidation occur

(b) Which electrode is the anode of the cell?
(c) Which electrode corrodes?
(d) Write the equation for the half- cell reaction at the anode?
(e) Write the equation for the half- cell reaction at the cathode?
(f) What is the emf of this galvanic cell when the switch is just
closed?

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Answer:

(a) Oxidation occurs at the zinc electrode since the zinc half- cell
reaction has a more negative E° potential of -0.763 V as
compared to -0.250 V for the nickel half- cell reaction.
(b) The zinc electrode is the anode since oxidation occurs at the
anode
(c) The zinc electrode corrodes since the anode in a galvanic cell
corrodes.
(d) Zn Zn2+ + 2e- E° = -0.763V
(e) Ni2+ + 2e- Ni E° =+0.250V
(f) The emf of the cell is obtained by adding the half- cell reactions
together:

Anode reaction: Zn Zn2+ + 2e- E° = -0.763 V

Cathode reaction: Ni2+ + 2e- Ni E° = +0.250 V

Overall reaction:Zn + Ni2+ Zn2+ + Ni E°cell = -0.513 V

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 2.5 Galvanic Cells Not 1 Molar Electrolytes

 Most electrolytes for real corrosion galvanic cells are

not 1 M, but are usually dilute solutions that are
much lower than 1 M.

 If the concentration of the ions in an electrolyte

surrounding an anodic electrode is less than 1 M, the
driving force for the reaction to dissolve or corrode
the anode is greater since there is a lower
concentration of ions to cause the reverse reaction

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 Nernst equation:

E = E° + 0.0592 log Cion

n

Where: E = new emf of half- cell

E° = standard emf of half- cell
n = number of electrons transferred
(for example, M Mn+ + ne-)
Cion = molar concentration of ions
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Problem 2:

A galvanic cell at 25ºC consist of an electrode of zinc in a 0.10 M

ZnSO4 solution and another of nickel in a 0.05 M NiSO4 solution.
The two electrodes are separated by a porous wall and connected
by an external wire. What is the emf of the cell when a switch
between the two electrodes is just closed?

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Answer:

 Half cell reactions:

Zn Zn2+ + 2e- E° = -0.763V (ANODE)

Ni Ni2+ + 2e- E° = -0.250V (CATHODE)

 Apply Nernst Equation:

Ecell = E° + 0.0592 log Cion

n
Anode reaction: EA = -0.763 V + 0.0592 log 0.10 = -0.793 V
2

Cathode reaction: Ec = - (- 0.250 V + 0.0592 log 0.05) = +0.289 V

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 Emf of the cell (Ecell) = EA + EC

= -0.793V + 0.289 V

= -0.505 V

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