Dr.

Fathy Shokry
Fathishoukry@[Link]

Lecture (1) Week 1

Course Objectives
• Detailed understanding of principles behind the corrosion of metals,
and methods for prevention, control, and experimentation. On
successful completion of this course, the student will be able to:
• Apply electrochemistry theories and principles to account for
corrosion causes, failures and prevention strategies
• Analyses a range of practical corrosion-related problems or
situations potentially impacted by corrosion and propose viable
and/or creative solutions
Course Objectives
• Acquire relevant corrosion-related data from the literature and
other sources, and interpret or re-interpret the data in synthesizing
practical reports
• Use professional language and technically accurate written work
to effectively communicate with corrosion engineers, operators
and managers
• Describe major corrosion testing methods and prevention
technologies, and explain their limitations
 Assessment Methods

Quizzes 10%
Projects/Reports/Others 15%
Mid-term Exam 15%
Final Exam 60%
Attendance
Attendance is compulsory, that means students who are more
than 25% absent will not be allowed to enter the final exam and
FAIL the course
References

1- Corrosion Engineering by Mars. G. Fontana.

2-Material Science and Engineering: an Introduction by William D-
Callister.
3- Principals of corrosion and protection by Stewart & Tulloch.
4- Handbook of Corrosion Engineering by Pierre R. Roberge .
Course Content
• Fundamentals of electrochemistry
• Structure of electrochemical interface
• Thermodynamics and Nernst Eqn.
• Kinetics of corrosion, polarization
• Electromotive series and Galvanic series
• Factors affecting corrosion
• Forms of corrosion
• Thermodynamics and kinetics of corrosion
• Corrosion control
 Course Title English
Code
Th. Tr. Pr.

Electrochemistry CHE 311 2 1 1

and its applications
Rules
Let us start our journey
Basics of Electrochemistry

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Galvanic Cell vs Electrochemical cell
• Galvanic cells derives its energy from spontaneous redox reactions,
while electrolytic cells involve non-spontaneous reactions and thus
require an external electron source like a DC battery or an AC power
source.
• Both galvanic and electrolytic cells will consist of two electrodes (an
anode and a cathode), which can be made of the same or different
metals, and an electrolyte in which the two electrodes are immersed.
Redox reactions
The term redox comes from “Reduction – Oxidation”.
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These are reactions involve transfer of electrons between chemical
species.
Note: the term chemical species refer to atoms, ions or molecules.

In oxidation reactions, an atom loses electron(s).

Oxidation number is an expression used by chemists to keep track
of how electrons are being shared within a chemical species.
Redox reactions

Oxidation reactions are associated with an increase in oxidation

number (or increase in the positive character “+ve” of the species.

Note: oxidation number for metals is zero.

Electrochemical Reactions
In electrochemical reactions, electrons are transferred from one species
to another.
Oxidation Numbers

In order to keep track

of what loses electrons
and what gains them,
we assign oxidation
numbers.
Oxidation and Reduction

• A species is oxidized when it loses electrons.

– Here, zinc loses two electrons to go from neutral
zinc metal to the Zn2+ ion.
Oxidation and Reduction

• A species is reduced when it gains electrons.

– Here, each of the H+ gains an electron and they
combine to form H2.
Oxidation and Reduction

• What is reduced is the oxidizing agent.

– H+ oxidizes Zn by taking electrons from it.
• What is oxidized is the reducing agent.
– Zn reduces H+ by giving it electrons.
Assigning Oxidation Numbers
Elements in their elemental form have an oxidation number
of 0.
The oxidation number of a monatomic ion is the same as its
charge.
Nonmetals tend to have negative oxidation numbers, although some
.
are positive in certain compounds or ions.
Oxygen has an oxidation number of −2, except in the peroxide ion in
which it has an oxidation number of −1.
Hydrogen is −1 when bonded to a metal, +1 when bonded to a
nonmetal.
Assigning Oxidation Numbers
Nonmetals tend to have negative oxidation numbers, although some
are positive in certain compounds or ions.
Fluorine always has an oxidation number of −1.
The other halogens have an oxidation number of −1 when they are
negative;
.
they can have positive oxidation numbers, however, most
notably in oxyanions.
The sum of the oxidation numbers in a neutral compound is 0.
The sum of the oxidation numbers in a polyatomic ion is the charge
on the ion.
Balancing Oxidation-Reduction Equations
•Perhaps the easiest way to balance the equation of an oxidation-reduction
reaction is via the half-reaction method.

•This involves treating (on paper only) the oxidation and reduction as two
separate processes, balancing these half reactions, and then combining them
to attain the balanced equation for the overall reaction.
Half-Reaction Method
1. Assign oxidation numbers to determine what is oxidized and
what is reduced.
2. Write the oxidation and reduction half-reactions.
3. Balance each half-reaction.
a. Balance elements other than H and O.
b. Balance O by adding H2O.
c. Balance H by adding H+.
d. Balance charge by adding electrons.
4. Multiply the half-reactions by integers so that the electrons gained
and lost are the same
5. Add the half-reactions, subtracting things that appear on both
sides.
6. Make sure the equation is balanced according to mass.
7. Make sure the equation is balanced according to charge.
Half-Reaction Method
Example (1)

Consider the reaction between MnO4− and C2O42− :

MnO4−(aq) + C2O42−(aq) ⎯⎯→ Mn2+(aq) + CO2(aq)

Half-Reaction Method
First, we assign oxidation numbers.
+7 +3 +2 +4

MnO4− + C2O42- ⎯⎯→ Mn2+ + CO2

Since the manganese goes from +7 to +2, it is reduced. Since the
carbon goes from +3 to +4, it is oxidized.
Oxidation Half-Reaction

C2O42− ⎯⎯→ CO2

To balance the carbon, we add a coefficient of 2:

C2O42− ⎯⎯→ 2 CO2

C2O42− ⎯⎯→ 2 CO2

The oxygen is now balanced as well. To balance the charge, we must add 2
electrons to the right side.
C2O 2− ⎯⎯→ 2 CO + 2 e−
4 2
Reduction Half-Reaction

MnO4− ⎯⎯→ Mn 2+

The manganese is balanced; to balance the

oxygen, we must add 4 waters to the right side.

MnO − ⎯⎯→ Mn2+ + 4 H O

4 2
Reduction Half-Reaction

MnO4− ⎯⎯→ Mn 2+ + 4 H2O

To balance the hydrogen, we add 8 H+ to the left side.

8 H+ + MnO4 − ⎯⎯→ Mn 2+ + 4 H2O

8 H+ + MnO4 − ⎯⎯→ Mn 2+ + 4 H2O

To balance the charge, we add 5 e− to the left side.

5 e− + 8 H+ + MnO4 − ⎯⎯→ Mn 2+ + 4 H2O

Combining the Half-Reactions
Now we evaluate the two half-reactions together:
C2O 2− ⎯⎯→ 2 CO + 2 e−
4 2
5 e− + 8 H+ + MnO − ⎯⎯→ Mn2+ + 4 H O
4 2
To attain the same number of electrons on each side, we will multiply the first
reaction by 5 and the second by 2.

5 C2O 2− ⎯⎯→ 10 CO + 10 e−
4 2
10 e− + 16 H+ + 2 MnO − ⎯⎯→ 2 Mn2+ + 8 H O
4 2
When we add these together, we get:

10 e− + 16 H+ + 2 MnO4 − + 5 C2O4 2− ⎯⎯→

2 Mn2+ + 8 H2O + 10 CO2 +10 e−
Combining the Half-Reactions

10 e− + 16 H+ + 2 MnO4 − + 5 C2O4 2− ⎯⎯→

2 Mn2+ + 8 H2O + 10 CO2 +10 e−

The only thing that appears on both sides are the electrons. Subtracting them, we are left
with:

16 H+ + 2 MnO4 − + 5 C2O4 2− ⎯⎯→

2 Mn2+ + 8 H2O + 10 CO2
Balancing in Basic Solution
• If a reaction occurs in basic solution, one can balance it as if
it occurred in acid.
• Once the equation is balanced, add OH− to each side to
“neutralize” the H+ in the equation and create water in its
place.
• If this produces water on both sides, you might have to
subtract water from each side.
Balancing Redox Equations

Example(2):

Cr2O72-(aq) + Fe+2 (aq) → Cr3+(aq) + Fe+3 (aq)

• How can we balance this equation?

• First Steps:
▪ Separate into half-reactions.
▪ Balance elements except H and O.

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0
 Balancing Redox Equation:
The Half-Reaction Method
• Write separate half-reactions for the oxidation
and the reduction processes.
 Balancing Redox Equation:
The Half-Reaction Method

• Cr2O72-(aq) → 2Cr 3+(aq)

+2 +3
• Fe (aq) → Fe (aq)

• Balance the atoms in the half-reactions other

than the hydrogen and oxygen.
 Balancing Redox Equation:
The Half-Reaction Method
• Balance oxygen atoms by adding water
molecules to the appropriate side of the equation.

2- 3+
Cr2O7 (aq) → 2Cr (aq) + 7 H2O (l)
 Balancing Redox Equation:
The Half-Reaction Method
• Then balance the hydrogen atoms:
2- 3+
• 14 H + Cr2O7 (aq) → 2Cr(aq) + 7 H2O (l)
+
 Balancing Redox Equation:
The Half-Reaction Method
• Adding electrons:
2- 3+
• 6e +14H Cr2O7 (aq) → 2Cr (aq) + 7H2O (l)
- +

• Fe +2(aq) → Fe +3 (aq) + e-
 Balancing Redox Equation:
The Half-Reaction Method
• Then equalize the electrons by multiplying
everything in one or both equations by a
coefficient.
• 6Fe +2(aq) → 6Fe +3 (aq) +6 e-
 Balancing Redox Equation:
The Half-Reaction Method
• Add the two half-reactions together. The electrons must
cancel. Balance any remaining substances by inspection. If
necessary, cancel out H2O or H+ that appear on both sides.
 Balancing Redox Equation:
The Half-Reaction Method
• Adding the hydroxide ions.
 Balancing Redox Equation:
The Half-Reaction Method
• Combining the hydrogen ions and hydroxide ions
to make water.
 Balancing Redox Equation:
The Half-Reaction Method
• Canceling out seven water molecules from both
sides to get the final equation
 Balancing Redox Equation:
The Half-Reaction Method
The equation is still balanced by atoms and by charge, but the
presence of hydroxide ions rather than hydrogen ions means that the
reaction takes place in basic solution. Typically, most redox reactions
will actually only proceed in one type of solution or the other. The
oxidation of Fe2+ by Cr2O72− does not occur in basic solution, and
was only balanced this way to demonstrate the method.
In summary, the choice of which balancing method to use depends on
the kind of reaction. The oxidation-number method works best if the
oxidized and reduced species appear only once on each side of the
equation and if no acids or bases are present. The half-reaction
method is more versatile and works well for reactions involving ions
in aqueous solution.