Corrosion of Metals

Thermodynamics of Corrosion

Corrosive Environments
Gaseous

Aqueous

dry corrosion

wet corrosion

Oxidation

Mechanism is

electrochemical

Electrochemical Cell

A device that generates electricity from a spontaneous REDOX

reaction
Electron transfer takes place through an external path way
rather than directly between reactants

Electrochemical Cell

Galvanic Cell
Spontaneous
Electrons flow freely

Electrolytic Cell
Reaction is non-spontaneous
Electron flow is forced

Electrochemical Reactions
Anodic Reactions
Oxidation of a metal into its ion
Characterized by loss of electrons
Number of electron produced = valence of ion
M Mn+ + neCathodic Reactions
Reduction
Characterized by consumption of electrons
2e- + 2H+ H2

Electrochemical Reactions
Example: Reduction of cupric ions by zinc
Cu2+ (aq) + 2eZn2+ (aq) + 2e-

Cu2+ (aq) + Zn (s)

Cu (s)
Zn (s)

Cu (s) + Zn2+ (aq)

1
2

Corrosion of between zinc and

hydrochloric acid

Zn

Zn2+ + 2eZn

2H+ + 2e-

H2 (gas)

Zn2+
Zinc

e-

Total reaction:
Zn + 2H+

Zn2+ + H2 (gas)

Zinc is metal and a good electrical conductor,

thus the electrons are transferred to an adjacent
reduction site and are used in the reduction of
hydrogen ions

eH+

H2

H+

10

Electrochemical Cells
Electrode Potential
A measure of the tendency of metals to oxidize or lose
electrons
Actually a measure of corrodability
Tables of Data
May be given in either standard reduction or standard
oxidation potentials
Higher Reduction Potential
More reducing, lower tendency to lose electrons, more
likely to act as cathode

Electrochemical Cells
Significance of the Cell Potential
Higher cell potential, more electrical work can be
done
If cell potential is zero, no work can be done
Thermodynamic Basis of the Cell Potential
Cell potential is related to G

G o
E =
nF
o

n, Number of
electrons involved in
the chemical reaction
F, Faradays Constant

= 23.06kcal/eV = 96,485 C/eV

Product of electron charge and

the number of particles in one
mole of a substance

Electrochemical Cells
Electrochemical Cell Potential
Also, electromotive force (EMF)
Calculated from the difference between the abilities
of the half-cells to attract electrons (electrode
potentials)
Equivalent to the work that the transfer of electrons
can accomplish

Standard Electrode Potential

Measured at STP and unit activity
Measured against SHE

E o cell = E o Cathode E o anode

Electrode potential
Taken as the difference
between the charge on the
electrode and the charge in
solution

Electrochemical Cell Potential

Difference in charge between the two electrodes
in terms of reduction potentials

Electrochemical Cells
Suppose a piece of copper metal is dropped into a test tube containing a solution
of silver nitrate. The solution turns blue. Complete the following table as an
exercise.
Electrode

Half-reaction

Eo, Volts

Anode

(1)

(1)2 +
Cu Cu
+ 2e

Cathode

(2)

Ag + + e(2)
Ag

Eored= +0.7991

Overall Rxn

Cu + 2 Ag + Cu 2+ + 2 Ag

Eocell= +0.4621

-(Eored)= -(0.337)

3. Calculate the electrochemical cell potential for the said reaction.

4. Which of the reactants is the oxidizing agent?

Eocell= +0.4621
Ag+ is the OA

Electrochemical Cells
Summary of steps in calculating the electrochemical cell potential:
1. Find two half reactions making up redox reaction.
2. Find Eo value for half-reactions from table of reduction potentials.
3. Reverse cell reaction with lower Standard Reduction Potential. This will be

oxidation half of redox reaction.

4. Balance electrons in two half reactions by multiplying one or both half reactions

with integers. Note: Eo values are not changed because number of electrons
transferred in redox reaction does not affect voltage difference.

5. Find sum of two half-reactions and Eo value for the cell.

6. For redox reaction to be spontaneous, the sum of the half-reactions must result in a

positive value for Eo cell.

+ 2e Cu

+ 2e Fe

o
= 0.440V
E red

+ 2e Zn

o
= 0.763V
E red

Cu 2
Fe 2
Zn 2

Fe

o
= +0.337 V
E red

e-

e-

Fe2+

Fe2+ solution

Cu

Cu2+

Cu2+ solution

Fe

Fe2+

Fe2+ solution

Zn

Zn2+

Zn2+ solution