Basic Concept of Corrosion: Part 1 Wk4

Corrosion cell
Anodic and cathodic reaction
Cell Potential
Electrode potential
Hydrogen Electrode
Concept on free energy
Nernst equation
Measurement of EMF and pH
Mathematical problems.
 Corrosion cell

Three basic types:

1. Dissimilar electrode cell: dissimilar metals

2. Concentration cell: two types

a) Salt concentration cell: difference in composition of
aqueous environment
b) Differential aeration cell: difference in oxygen
concentration

3. Differential temperature cell: difference in

temperature distribution over the body of the metallic
materials
 Corrosion cell

i. Dissimilar electrode cell

 Corrosion cell

2a. Salt concentration cell:

Copper dissolves from the electrode in

contact with the dilute solution (anode)

Plates out on the other electrode in

concentrated (cathode)

Both reactions tend to bring the solutions

to the same concentration.
2b. Differential aeration cell:

The aerated electrode is cathode

De-aerated electrode is anode

The difference of oxygen

concentration produces a potential
difference and causes current flow.

Crevice corrosion
3. Differential temperature cell:

Same metal but in two different temp

The hot pipe near the compressor is the anode
The cooler pipe down the line is the cathode

The soil is the electrolyte
The pipe itself is the connecting circuit

Concentration cell resulting from heat differential

Gas transmission line:

Differential temperature cell:
- Found in heat exchanger, boilers, immersion heaters
- Depends on the type of metal/environment

Copper in CuSO4 solution :

Electrode at higher temperature - cathode
Same for lead
Electrode at lower temperature Anode

Reverse: Silver and iron

But for iron: after a matter of hours, depending on

aeration, stirring rate and weather; the polarity can be
reversed.
Anodic and cathodic reaction
Reaction at anode:
Oxidation takes place with the releasing of electrons.

At anode:
Fe Fe2+ + 2 e-
(indicating rough surface)

Positively charged iron atoms get detached from the solid

surface and enter in to solution (electrolyte) as positive
ions.
 Anodic and cathodic reaction

Anodic reaction:
Reaction at cathode:

It occurs with the taking up of electrons.

At Cathode:
2 H+ + 2e- H2
(indicating by formation of bubbles at the surface)

The free electrons reach at the cathode and react

with some positively charged species such as
hydrogen ions in the electrolyte solution.

In the absence of acid, water itself dissociates to

generate H+ ions.
Cathodic reaction:
 5 Reduction Reactions (Consume electrons)

i. Hydrogen Evolution: 2H+ + 2e- H2

ii. Oxygen Reduction (acid): O2 + 4H+ + 4e- 2H20

iii. Oxygen Reduction (neutral or basic):

O2 + 2H2O + 4e- 4OH

iv. Metal Ion Reduction: M3+ + e- M2+

v. Metal Deposition: M+ + e- M
Source: http://www.jesuitnola.org/upload/clark/refs/red_pot.htm
Galvanic series is an arrangement of both metals and
alloys according to their actual measured potentials in
particular environment. There could be individual galvanic
series for each environment.
 Anodic and cathodic reactions are coupled at a
corroding metal surface.

Zn Anode
Oxidized
Active

Pt Cathode
Reduced
Passive

Zn Zn2+ + 2e - (oxidation)
Pt 2+ + 2e- Pt (Reduction)
Zn + Pt 2+ Zn2+ + Pt (Overall)
Anodic and cathodic reactions are coupled at a
corroding metal surface.
Dry cell

Overall: Zn (s) + 2MnO2(s) ZnO (s) + Mn2O3(s)

Convention for expressing the cell:

Anode Half-Cell || Cathode Half-Cell

Electrode | Anode Soln || Cathode Soln | Electrode

Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)

Pt(s) | H2 (1 atm) | H+ (1 M) || Fe3+(aq), Fe2+(aq) | Pt(s)

Electrons flow from anode to cathode. Anode is placed on left

by convention.
 Anode Half-Cell || Cathode Half-Cell
Electrode | Anode Soln || Cathode Soln | Electrode

Pt H2 (g) H+ (aq) Cu2+ (aq) Cu (s) Pt

Electrochemical cells
a cell that has not reached equilibrium and can
do electrical work by driving electrons through
an external wire.
Basic Concept of Corrosion: Part 1

Corrosion cell
Anodic and cathodic reaction
Cell Potential
Electrode potential
Hydrogen Electrode
Concept on free energy
Nernst equation
Measurement of EMF and pH
Mathematical problems.
 Cell potential

Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)

Anode Half-Cell || Cathode Half-Cell
SHE: 2H+(aq) + 2e- H2(g) E0= 0.0000

Zn2+(aq) + 2e- Zn(s) E0= -0.7618

Cu2+(aq) + 2e- Cu(s) E0= 0.52

 Electrode potential

Electrode potential, E is an electromotive force of a

cell/electrode

Electrode potential of a metal is measured (in volts)

in a solution containing an unit concentration of the
ions of the same metal with respect to standard
hydrogen electrode as the counter electrode (whose
potential is zero).

It appears at the interface between an electrode

and electrolyte due to
i. the transfer of charged species across the interface,
ii. specific adsorption of ions at the interface, and
iii. specific adsorption/orientation of polar molecules,
including those of the solvent.
 The value of the electrode potential under non-equilibrium
depends on the nature and composition of the
contacting phases, and on the kinetics of electrode
reactions at the interface.

The measured potential could be either

i. reversible potential (at equilibrium on the working
electrode)
ii. mixed potential (a potential with a non-zero net
reaction on the working electrode but zero net
current (corrosion potential), or
iii. galvanic corrosion or voltammetry (a potential with
a non-zero net current on the working electrode)
 Hydrogen Electrode
Since absolute potentials of electrodes are not known, it is
convenient to assume arbitrarily that the standard potential for
the reaction is equal to zero at all temperatures.

Standard Hydrogen Electrode/SHE: potential of a platinum

electrode in 1 m H+ solution with 1 atm and 25C.

This is used as reference and E = 0

All other oxidations are compared to E = 0 H2

Pt
indicates standard states of
25C, 1 atm, 1 M solutions.

H+
 Standard hydrogen electrode (SHE) (E=0.000 V) activity of H+=1

Its absolute electrode potential is estimated to be 4.44 0.02 V at 25 C, but to

form a basis for comparison with all other electrode reactions, hydrogen's standard
electrode potential (E0) is declared to be zero at all temperatures.

The scheme of the standard hydrogen electrode:

1. Platinized platinum electrode

2. hydrogen blow
3. solution of the acid with activity of H+ = 1 mol dm3
4. hydroseal for prevention of the oxygen interference

5. reservoir through which the second half-element of the

galvanic cell should be attached. The connection can be
direct, through a narrow tube to reduce mixing, or through a
salt bridge, depending on the other electrode and solution.
This creates an ionically conductive path to the working
electrode of interest.
Basic Concept of Corrosion: Part 1

Corrosion cell
Anodic and cathodic reaction
Cell Potential
Electrode potential
Hydrogen Electrode
Concept on free energy
Nernst equation
Measurement of EMF and pH
Mathematical problems.
 Concept on free energy

Free energy is the internal energy of a system minus the

amount of energy that cannot be used to perform work.

This unusable energy is given by the entropy (S) of

a system multiplied by the temperature (T) of the
system.

Free energy could be defined in two ways:

i. Helmholtz free energy
ii. The Gibbs free energy
Helmholtz free energy is defined as F = U TS
where U is the internal energy,
T is the absolute temperature, and
S is the entropy.

Gibbs free energy: G = H TS

where H is the enthalpy.
(H = U + pV, where p is the pressure and V is the volume.)

In physics, free energy most often refers to the

Helmholtz free energy, denoted by A,

while in chemistry, free energy most often refers to the

Gibbs free energy.
 Gibbs Free Energy:
The tendency for a chemical reaction to go.
The tendency of a reaction with the environment is
measured by the Gibbs free-energy change G.
The more negative the value of G, the greater is the
tendency for the reaction to go.

Mg + H2O (l) + 1/2O2 (g) Mg(OH)2 (S) G = - 142 kCal

Cu + H2O (l) + 1/2O2 (g) Cu(OH)2 (S) G = - 28.6 kCal

As compared to Cu,
Mg has higher tendency to react with water and oxygen.
 Gibbs free energy

Free energy of formation for some metal oxides at 25oC (KJ/mole)

Al2O3 Cr2O3 Ti2O Fe2O3 MgO NiO Cu2O Ag2O Au2O3
1576 1045 853 740 568 217 145 13 +163

Characteristics of oxides:
Oxide is the more stable than the metal (for most metals)
Oxidation rate becomes significant usually at high
temperatures
The nature of the oxide determines the rate of oxidation
 Gibb's Energy and Electric Energy

In electrochemical corrosion, the tendency for a metal to

corrode can be expressed in terms of the electromotive
force (emf) of the corrosion cells.

G = - EnF

E is emf in volts, n is number of electron (or chemical

equivalents), F is Faraday (96,500 C/eq).
 What are reaction quotients, equilibrium constants, and the mass action
law?

A general reaction of a moles of A and b moles of B to produce c moles

of C and d moles of D can be represented by

aA+bB=cC+dD

Activities of A, B, C, and D are represented by {A}, {B}, {C} and {D}

respectively.

In any system, the reaction quotient is defined by Q

Q tends to approach a constant K for a given reaction in a closed
system. Such a state is called equilibrium.

K is called the equilibrium constant. The constant K depends on

temperature and the nature of the reactants and products.

This is known as the mass action law.

 What are the relationships between the Gibb's free energies and
the equilibrium constants?

Free Energy is the driving force for reactions.

The tendency for a reaction to reach a equilibrium is driven by
the Gibbs free energy, Go and the relationship has been
defined by the relationship

Go = - R T ln K

If K > 1, then the forward reaction is spontaneous.

When the Gibb's energy is negative, the reaction is spontaneous.

A reaction (change) is the result of a system trying to minimize its Gibb's

free energy, Go changes from 0 to - R T ln K as the system changes
from standard condition to an equilibrium state.
Anodic and cathodic reaction
Anodic and cathodic reaction
Basic Concept of Corrosion: Part 1

Corrosion cell
Anodic and cathodic reaction
Cell Potential
Electrode potential
Hydrogen Electrode
Concept on free energy
Nernst equation
Measurement of EMF and pH
Mathematical problems.
 Nernst Equation

Nernst Equation and Calculation of Half-Cell potential

Nernst Equation
Nernst Equation
Nernst Equation
 Nernst Equation

Take the expression for the Gibbs dependence on activity and turn this
around for an expression in terms of the cell potential.

G G RT ln Q

The relation between cell potential E and free energy gives

n F E n F E RT ln Q

Rearrange and obtain the Nernst Equation.

RT
E E ln Q
nF
Nernst Equation
The equation is sometimes streamlined by restricting discussion to T =
25 C and inserting the values for the constants, R and F.

0.0257
E E ln Q R = 8.314 J/deg- mole
n F = 96500 C/eq
0.0592
E E log Q lnQ = 2.303logQ
n

Note the difference between using natural logarithms and base10 logarithms.
Basic Concept of Corrosion: Part 1

Corrosion cell
Anodic and cathodic reaction
Cell Potential
Electrode potential
Hydrogen Electrode
Concept on free energy
Nernst equation
Measurement of EMF and pH
Mathematical problems.
 Calculation of Cell Potential

p.28 (Uhlig):
Table 2
Pt 2+ + 2e- Pt +1.2V
Mg 2+ + 2e - Mg -2.363V

Actual Actual
Mg Mg 2+ + 2e - (oxidation) +2.363V
Pt 2+ + 2e - Pt +1.2V
Actual Actual
Mg Mg 2+ + 2e - (oxidation) +2.363V
Pt 2+ + 2e - Pt +1.2V
Total Total
Mg + Pt 2+ + 2e - Mg 2+ + 2e - + Pt +3.563V
 How does Ecell dependend on concentration?

Recall, in general:
G = G + RTln(Q)
However:
G = -nFEcell
-nFEcell = -nFEcell + RTln(Q)

Ecell = Ecell - (RT/nF)ln(Q)

Ecell = Ecell - (0.0591/n)log(Q)

The Nernst Equation
 With the Nernst Eq., we can determine the effect of
concentration on cell potentials.

Ecell = Ecell - (0.0591/n)log(Q)

Example 1: Calculate the cell potential for

the following:

Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s)

Where [Cu2+] = 0.3 M and [Fe2+] = 0.1 M

 First, need to identify the 1/2 cells

Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s)

Cu2+(aq) + 2e- Cu(s) E1/2 = 0.34 V

Fe2+(aq) + 2e- Fe(s) E1/2 = -0.44 V

Fe(s) Fe 2+(aq) + 2e- E1/2 = +0.44 V

Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s) Ecell = +0.78 V

Now, calculate Ecell

Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s) Ecell = +0.78 V

Ecell = Ecell - (0.0591/n)log(Q)

Q
Fe 2

(0.1)
0.33
Cu (0.3)
2

Ecell = 0.78 V - (0.0591 /2)log(0.33)

Ecell = 0.78 V - (-0.014 V) = 0.794 V
 Concentration and Ecell

Example 2: If [Cu2+] = 0.3 M, what [Fe2+] is needed

so that Ecell = 0.76 V?

Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s) Ecell = +0.78 V

Ecell = Ecell - (0.0591/n)log(Q)

0.76 V = 0.78 V - (0.0591/2)log(Q)
0.02 V = (0.0591/2)log(Q)

0.676 = log(Q)
4.7 = Q
Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s)

4.7 = Q

Q

Fe 2

4.7
Cu 2

Q
Fe 2

4.7
0.3

[Fe2+] = 1.4 M

Concentration Cells (cont.)

Ag+ + e- Ag E1/2 = 0.80 V

What is the cell potential if both

sides had 1 M concentrations of Ag+?

E1/2 would be the same;

therefore, Ecell = 0.
 Anode: Ag Ag+ + e- E1/2 = -0.8 V

Cathode: Ag+ + e- Ag E1/2 = 0.80 V

What is Ecell?

Q
Ag

anode

0.1
0.1
Ag
cathode
1

Ecell = Ecell - (0.0591/n)log(Q)

0V
1

Ecell = - (0.0591)log(0.1) = 0.0591 V

What is Ecell?
e- Ecell = Ecell - (0.0591/n)log(Q)
0 2

Fe2+ + 2e- Fe
2 e- transferredn = 2

Q
Fe
2
anode

0.01
0.1
Fe
2
cathode
.1
anode cathode

Ecell = -(0.0296)log(.1) = 0.0296 V
 Concentration and Ecell
STANDARD EMF SERIES
EMF series Metal with smaller Vo corrodes.
o
Vmetal
metal
Au +1.420 V
- +
Cu +0.340
Pb - 0.126
more cathodic

Sn - 0.136 V o =
Ni - 0.250 0.153V
Cd 25C Ni
Co - 0.277
Cd - 0.403
Fe - 0.440 1.0 M 1.0 M
Cr - 0.744 Cd 2 + solution Ni 2+ solution
more anodic

Zn - 0.763
Al - 1.662
Mg - 2.363
Na - 2.714
K - 2.924
60
 pH = - log10[H+] pOH = - log10[OH-]

Pure water has a pH of 7

Strong acids have lower pHs which

means they have more H+ ions!

Strong alkalis have low pOHs which

means they have more OH- ions!

The more ions, the more toxic the

solution.

Figure 1. The scales of pH and pOH.

The Nernst equation is used to calculate the voltage of an
electrochemical cell or to find the concentration of one of the
components of the cell.

Ecell = E0cell - (2.303*RT/nF)logQ

Ecell = E0cell - (RT/nF)lnQ

Ecell = cell potential under nonstandard conditions (V)

E0cell = cell potential under standard conditions
R = gas constant, which is 8.31 (volt-coulomb)/(mol-K)
T = temperature (K)
n = number of moles of electrons exchanged in the electrochemical reaction
(mol)
F = Faraday's constant, 96500 coulombs/mol
Q = reaction quotient, which is the equilibrium expression with initial
concentrations rather than equilibrium concentrations
Ex. 1: A zinc electrode is submerged in an acidic 0.80 M Zn2+
solution which is connected by a salt bridge to a 1.30 M Ag+ solution
containing a silver electrode. Determine the initial voltage of the cell
at 298K.

Unless you've done some serious memorizing, you'll need to consult the
standard reduction potential table, which will give you the following
information:

E0red: Zn2+aq + 2e- Zns E = -0.76 V

E0red: Ag+aq + e- Ags E= +0.80 V

Ecell = E0cell - (0.0591 V/n)log Q

Q = [Zn2+]/[Ag+]2
 Mathematical Problem
The reaction proceeds spontaneously so E0 is positive. The only way for that to occur is if Zn is
oxidized (+0.76 V) and silver is reduced (+0.80 V). Once you realize that, you can write the
balanced chemical equation for the cell reaction and can calculate E0:

Zns Zn2+aq + 2e- and E0ox = +0.76 V

2Ag+aq + 2e- 2Ags and E0red = +0.80 V

which are added together to yield:

Zns + 2Ag+aq Zn2+a + 2Ags with E0 = 1.56 V

Q = [Zn2+]/[Ag+]2
Q = (0.80)/(1.30)2
Q = (0.80)/(1.69)
Q = 0.47
Now, applying the Nernst equation: Ecell = E0cell - (0.0591 V/n)log Q
E = 1.56 V - (0.0591 / 2)log(0.47)
E = 1.57 V
Ex. 2: Determine the cell voltage by considering the reaction of tin and
bromine when the concentrations of tin(II) and tin(IV) are 0.050 M and
0.00010 M respectively and the concentration of bromide is 0.00010 M.

Sn2+(aq) + Br2 (l) Sn4+(aq) + 2 Br-(aq) E0 = 0.92 V

Q = [Sn4+][Br-]2 / [Sn2+]

The Nernst equation for this reaction is:

0.0591V [Sn4+] [Br-]2
E = 0.92 V - ------- log( ------------ )
2 [Sn2+]
0.0591V (0.00010 M)(0.00010 M)2
E = 0.92 V - ------- log( ----------------------- )
2 0.050 M
0.0591V
E = 0.92 V - ------- log(2.0x10-11)
2
E = 0.92 V - (-0.316 V)
E = 1.24 V
 Mathematical Problem

Ex. 4: The emf of a cell made up of zinc (anode) and hydrogen electrode
(cathode) immersed in 0.5M ZnCl2 is + 0.590 V. What is the pH of the
solution?
Zn(s) Zn2+(aq) + 2e- (oxidation reaction) E0= 0.763
2H+(aq) + 2e H2(g) (reduction reaction) E0= 0.000
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) (overall reaction) E0= 0.763

Q = [Zn2+][PH2] / [H+]2

The Nernst equation for this reaction is:

0.0591V [Zn2+][PH2]
E = 0.763 V - ------- log(---------)
2 [H+]2

0.0591V 0.5 x 1
0.590 = 0.763 V - ------- log(---------)
2 [H+]2

-0.173 = - 0.02955 [ -0.301 2log [H+] ]

- 2log [H+] = 6.155 -log [H+] = pH = 3.07
 Mathematical Problem

Ex. 5: Calculate the theoretical tendency of zinc to corrode (in volts) with
the evaluation of hydrogen when immersed in 0.01M ZnCl2 acidify to
pH=2.
Zn(s) Zn2+(aq) + 2e- (oxidation reaction) E0= 0.763
2H+(aq) + 2e H2(g) (reduction reaction) E0= - 0.000
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) (overall reaction) E0= 0.763

Q = [Zn2+][PH2] / [H+]2

Here, pH = - log [H+] = 2

[H+] = 0.01
The Nernst equation for this reaction is:

0.0591V [Zn2+][PH2]
E = 0.763 V - ------- log(---------)
2 [H+]2

0.0591V 0.01 x 1
E = 0.763 V - ------- log(---------)
2 (0.01)2

E = 0.704 V
What is the potential in the cell if [Cu2+] = 0.01 M and [Zn2+] =
1.00 M? Ans: 1.041 V
Questions for active learning:
1. What is corrosion cell? Give example for different forms of
corrosion cell.
2. Explain the anodic and cathodic reactions.
3. Write a short note on: i) Electrode potential, ii) Hydrogen
Electrode, iii) Gibbs free energy, iv) mass action law, v) Nernst
equation.
4. Explain the following reference electrodes: i) Saturated calomel
electrode, ii) Silver chloride electrode.
5. Maths: Given examples + Uhligh: Chapter 3, Exercise 1-10
(page 392).
Appendix A: STANDARD POTENTIALS