UMIST

Corrosion and Protection Centre

Module 0 Introduction to Corrosion

Module Notes Chemistry and Electrochemistry

September 2003

Module 0, Chemical and Electrochemical Reactions - Page 2 2002 - 2003, UMIST

This document is 2002 - 2003, the Corrosion and Protection Centre, UMIST.

All rights reserved

Chemistry and Electrochemistry
Learning outcomes at the end of the course you should be able to

Distinguish between chemical and electrochemical reactions

Give examples of chemical and electrochemical reactions

Balance chemical and electrochemical reactions

Before we consider chemical reactions, you need to be aware of a number of terms that
are used in chemistry. If you are unfamiliar with these, then we suggest that you look at
the relevant sections in Corrosion, by Shrier et al., or the links given in the Resources
section of the WebCT site, to learn a little more about them:

Atom In simple terms atoms consist of a central nucleus that has a positive charge,
surrounded by negatively charged electrons that orbit around the nucleus.
Atoms are the fundamental building blocks of chemistry atoms can be
changed in nuclear reaction, but they are not changed in chemical reactions,
except by small changes in the outer (valance) electrons.

Element The chemical nature of an atom is determined by the number of electrons that
orbit the nucleus, and hence by the charge on the nucleus. An element is a
mass composed of atoms with all the same charge on the nucleus.

Molecule A molecule is a collection of atoms held together by chemical bonds (usually

covalent).

Ion An ion is an atom or molecule that has lost or gained one or more electrons,
such that it has a net negative or positive charge. Ions that have lost electrons
are positively charged and are known as cations (e.g. sodium ions, Na+, and
ammonium ions, NH4+). Ions that have gained electrons are negatively
charged, and are known as anions (e.g. chloride ions, Cl-, or sulphate ions,
SO42-).

Bonds Chemistry is largely about the ways in which atoms can join together to form
molecules, crystals and other structures. Chemical bonds are a result of
interactions between the outer electrons in the atoms. Covalent bonds result
when electron pairs are shared between two atoms, normally with one electron
of the pair coming from each atom. Ionic bonds are produced when anions
and cations are held together by electrostatic forces, usually in an ionic
crystal. The metallic bond results from a distributed sharing of electrons
between many atoms. The easy movement of electrons within a metal crystal
is the cause of the characteristic good electrical conductivity of metals.

2002 - 2003, UMIST Module 0, Chemical and Electrochemical Reactions - Page 1

Chemical reactions
Chemical reactions occur when one or more reactants (which may be atoms, molecules or
ions), combine to produce one or more products.

Chemical reactions only involve changes in the bonding between the atoms that are
involved, and the number of atoms of the various elements will not change.

Chemical reactions may occur between species dissolved in a liquid (including the liquid
itself) in a gas mixture, between components of a solid solution or at the interface
between solids and liquids, gases or other solids. Reactions occurring within a single
phase (gas, liquid or solid) are known as homogeneous reactions, while reactions
occurring at the interface between two phases are known as heterogeneous reactions. As
a general rule homogenous reactions occur more easily than heterogeneous reaction,
because they can occur throughout the volume, rather than occurring only at the
boundary. However, solid surfaces may assist in the reaction, or catalyse it.

Chemical reactions may involve a transfer of electrons from one species to another, but
overall they will not involve a change in the number of electrons.

Types of chemical reaction

Chemical reactions may be classified in a number of types, and some of the common
reaction types are summarized in Table 1, which also gives examples of each type of
reaction:

Table 1 Types of chemical reaction and examples

Type of Reaction General form and examples

Synthesis A+B AB
Fe + Cl2 FeCl2
2H2 + C CH4
Combustion nA + O2 2An/2O
CH4 + 2O2 CO2 + 2H2O
Decomposition AB A+B
2NaHSO3 Na2SO3 + H2O + SO2
Replacement A + BC AB + C
2KBr + Cl2 2KCl + Br2
Hydrolysis A + H2 O AOH- + H+
3+
Al + 3H2O Al(OH)3 + 3H+

Electrochemical reactions
Electrochemical reactions are heterogeneous reactions that involve the transfer of charge
from a chemical species in solution to a metal. As the charge carriers in a metal are
electrons, whereas free electrons cannot exist in solution (with a few rather rare
exceptions, such as liquid ammonia), electrochemical reactions may be thought of as
reactions that produce or consume electrons.

Module 0, Chemical and Electrochemical Reactions - Page 2 2002 - 2003, UMIST

Reactions that produce electrons result in the oxidation of the species in solution and are
known as anodic reactions. Reactions that consume electrons result in the reduction of
the species in solution, and are know as cathodic reactions. Examples of anodic and
cathodic reactions are given in Table 2.

Table 2 Example electrochemical reactions

Type of Reaction Examples

Anodic Fe Fe2+ + 2e-

Zn Zn2+ + 2e-
Fe2+ Fe3+ + e-
4OH- O2 + 2H2O + 4e-
Cathodic O2 + 2H2O + 4e- 4OH-
2H2O + 2e- H2 + 2OH-
Fe3+ + e- Fe2+

Note that for every anodic reaction there is a cathodic reaction that is the reverse (see the
two examples in Table 2).

Balancing Reactions
Chemical and electrochemical reactions involve changes in the bonding of atoms,
molecules or ions, and there is no change in the chemical species present. Consequently,
when we write the equation for a chemical reaction, we must have the same number of
atoms of each species on each side of the equation. For chemical reactions we must also
have the same net charge on each side of the equation; this is also true for
electrochemical reactions, providing we include electrons in the calculation of the charge.
Balancing a chemical reaction is the process of adjusting the numbers of each molecule,
atom and ion on each side of a reaction such that the above requirements are met. To take
and example, we may remember that a common cathodic electrochemical reaction is the
reduction of dissolved oxygen. This is an electrochemical reaction, so we know that it
consumes electrons, and we remember that the reaction produces hydroxyl ions, so we
can write the reaction as:

aO2 + bH2O + c e- = dOH-

Balancing the reaction then involves the determination of a, b and c such the numbers of
oxygen and hydrogen atoms are the same on each side of the reaction, and that the net
charges are the same. This translates to a set of simultaneous equations:

Oxygen 2a + b = d
Hydrogen 2b = d
Charge c = d

With only three equations and four unknowns there are an infinite number of solutions,
but we normally aim for the smallest solution for which all the numbers are integers, in
this case a = 1, b = 2, c = 4, d = 4, leading to:

O2 + 2H2O + 4e- = 4OH-

2002 - 2003, UMIST Module 0, Chemical and Electrochemical Reactions - Page 3
Some authors will permit fractional values, so this reaction may also be written as:

O2 + H2O + 2e- = 2OH-

Then the general approach to constructing and balancing a chemical equation is:

1. Work out which species are likely to be present on each side of the equation.
It may involve some guesswork or trial and error to decide where to place
species such as water, but it doesnt really matter if you have water on the
wrong side of the equation you will find that you need a negative number of
water molecules to balance the equation, so you can shift it to a positive
number on the other side.

2. Work out the numbers of each species that need to be present to cause the
same number of atoms and the same quantity of charge to be present on each
side of the equation. This can usually be done by inspection.

Module 0, Chemical and Electrochemical Reactions - Page 4 2002 - 2003, UMIST

 2002 - 2003, UMIST Module 0, Chemical and Electrochemical Reactions - Page 5