What is corrosion? Why metals corrode?

Where Periodic table comes

in picture? How corrosion can be predicted? What is oxidation and
reduction number and what do they tell us in corrosion?
Let us start from definition of corrosion and build thoughts on it.

What is corrosion?

Definition [Wikipedia]: Corrosion is a natural process that converts a refined

metal into a more chemically-stable form such as oxide, hydroxide, or sulfide. It
is the gradual destruction of materials (usually metals) by chemical and/or
electrochemical reaction with their environment.

Following are important words in the definition to remember:

[1] corrosion products are as oxide, hydroxide, or sulfide and [2] Corrosion
happens by chemical and/or electrochemical reactions corrosion products are as
oxide, hydroxide, or sulfide

Why metals corrode?

Metals occur in nature most commonly as oxide or sulphide ores. Extraction of

the metal from its ore involves reduction of the oxidized form to free metal. It is
the general tendency of metals to go back to their original stable form and
become oxidized again, through loss of electrons. When metal loose electrons or
oxidized, it also loses metal, M ---- > M++ + 2e-. This oxidizing tendency of a
metal is the driving force for corrosion virtually all metals except the very noble
metals such as gold or platinum undergo some oxidation corrosion. Gold and
platinum are highly unreactive metals Gold and platinum oxides are highly
unstable, Gold and platinum oxides decompose back to metal and O2. Gold and
platinum do not undergo oxidation corrosion. Where there is sulfur, like in oil and
gas production, the chemical degradation of metal/alloy components in sulfur
environment is a major concern.

Important line on above paragraph is ‘This oxidizing tendency of a metal is the

driving force for corrosion’
What is oxidizing tendency of metals?

Metals oxidize because they want to go back to their stable form oxides by losing
electrons.

4Fe + 3O2 → 2Fe2O3

In above equation each Fe atom has lost 3 electrons = 3*4 = 12 electrons lost by
iron. Each O atom has gained 2 electrons = 2*6=12

Fe --- > Fe+++ + 3e- and O2 has gained two electrons, O2 + 2e- --- > 2O - -

Why oxides are stable form of Iron?

Role of Periodic table comes here:

Iron loses electrons to come to stable energy level in the form of oxides.

What is energy level?

Energy level of an atom is the distance of its outer shell electrons from nucleus.
The larger the number of the energy level, the farther it is from the nucleus. In
other words, farthermost from protons in nucleus which hold the electrons in the
orbit. Electrons that are in the highest energy level are called valence electrons.
An atom will lose electrons first which are at their highest energy level.

Iron’s valence electrons

Iron can lose three electrons form its highest energy level [not
going into details which may be too complex for this post] and
can form stable oxides by process of reduction in presence of
Oxygen. This is what iron does. This is fundamental to
corrosion of iron.
Recap: What is oxidation and reduction

Oxidation is the loss of electrons or an increase in the oxidation state of an atom

by a molecule, an ion, or another atom. Reduction is the gain of electrons or a
decrease in the oxidation state of an atom by a molecule, an ion, or another
atom. An oxidizing agent is a substance which makes other to lose electrons and
gains those electrons to get reduced. A reducing agent is a substance which loses
electrons and gets oxidized. This is very important to understand corrosion.

Where role of Periodic table comes in corrosion?

Metals lose electrons and called electropositive in nature to come to a lower

energy state. Non-metals gain electrons to come to a stable atomic structure and
are known as electronegative in nature. For example, Na has atomic number 11
with 11 electrons and 11 protons. In its outer valance shell there is just 1 electron.
To achieve a stable structure with 8 electrons in outer shell, it has two options [1]
lose 1 electron or [2] to gain 7 electrons. Option [2] is not possible because it has
only 11 protons. Therefore, Na loses 1 electron and acquire a +ve charge and that
becomes its combining power which we call valance. Similarly for Cl , atomic
number 17, there are 17 electrons and 17 protons. Cl has 7 electrons in outer
shell. Cl has two options [1] to gain 1 electron and come to stable state of 8
electrons in outer shell or [2] lose 7 electrons. Option [2] does not give it stability
because it has 17 protons. Therefore it opts to lose 1 electron to achieve a stable
state with one –ve charge which becomes its valence.

The periodic table has the elements arranged in order of increasing atomic
number. A vertical column, called a group, contains elements with similar
properties. A period runs from left to right with the atomic number of the
elements increasing from left to right.

I repeat, metals are electropositive and non-metals are electronegative in nature.

On the periodic table, electronegativity generally increases as you move from left
to right across a period and decreases as you move down a group. As a result, the
most electronegative elements are found on the top right of the periodic table,
while the least electronegative elements are found on the bottom left.

The opposite of electronegativity is electropositivity. It is a measure of an

element's ability to donate electrons.

All metals exhibit a tendency to be oxidized, some more easily than others. A
tabulation of the relative strength of this tendency is called the galvanic series.
Knowledge of a metal's location in the series is an important piece of information
to have in making decisions about its potential usefulness for structural and other
applications. The thermodynamic or chemical energy stored in a metal or that is
freed by its corrosion varies from metal to metal. It is relatively high for metals
such as magnesium, aluminum, and iron, and relatively low for metals such as
copper, silver and gold. The following Table lists a few metals in order of
diminishing amounts of energy required to convert them from their oxides to
metal.
What does this table mean to corrosion?

Within metals lithium [Li] has the maximum stored energy to release to come to a
stable energy level by losing electrons. Lithium is most electropositive metal.
Theoretically lithium will have the fastest rate of corrosion and gold has least
corrosion rate.

Oxidation state of metals and corrosion [Short introduction]

Definition: Wikipedia

The oxidation state, sometimes referred to as oxidation number, describes the

degree of oxidation (loss of electrons) of an atom in a chemical compound.
Conceptually, the oxidation state, which may be positive, negative or zero, is the
hypothetical charge that an atom would have if all bonds to atoms of different
elements were 100% ionic, with no covalent component.

What does it mean?

It tells us in simple words in a redox reaction which element got oxidized and
which element got reduced by assessing the change in oxidation number during
the reaction. Generally, the oxidation number (also called oxidation state) is an
integer which can be positive, negative, or zero. Oxidation number of an atom or
molecule which has no charge is taken as zero. Metals have positive oxidation and
non-metals have negative oxidation number. Sum total of all oxidation numbers
in a molecule is zero. Oxidation is gain of oxidation state or increase in oxidation
number. Reduction is losing oxidation state or decreasing oxidation number.

In image below some typical oxidation numbers are given in yellow

Example

Let us take a simple red-ox reaction

Cl2 + Fe ---- > FeCl2

Cl2 a neutral molecule with zero oxidation number goes to, 2 x [-1] = [-]2 , that
means chlorine is getting reduced. Fe, a neutral atom with no charge, with
oxidation number
zero goes to [+2], to produce a neutral molecule FeCl2, with sum total oxidation
numbers equal to zero. That signifies iron got oxidized in the reaction by chlorine.