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Page 2 © 2002 . UMIST Corrosion and Protection Centre Module 0 – Introduction to Corrosion Module Notes – Chemistry and Electrochemistry September 2003 Module 0.2003. UMIST . Chemical and Electrochemical Reactions .

This document is © 2002 . UMIST. the Corrosion and Protection Centre. All rights reserved .2003.

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but they are not changed in chemical reactions. The easy movement of electrons within a metal crystal is the cause of the characteristic good electrical conductivity of metals. by Shrier et al. and ammonium ions. Cl-. or the links given in the Resources section of the WebCT site. NH4+). normally with one electron of the pair coming from each atom. Ions that have gained electrons are negatively charged. Ions that have lost electrons are positively charged and are known as cations (e.. SO42-). © 2002 . chloride ions. Molecule A molecule is a collection of atoms held together by chemical bonds (usually covalent). Atoms are the fundamental building blocks of chemistry – atoms can be changed in nuclear reaction. If you are unfamiliar with these. Chemical bonds are a result of interactions between the outer electrons in the atoms. The metallic bond results from a distributed sharing of electrons between many atoms. Covalent bonds result when electron pairs are shared between two atoms. such that it has a net negative or positive charge.g. to learn a little more about them: Atom In simple terms atoms consist of a central nucleus that has a positive charge. Ion An ion is an atom or molecule that has lost or gained one or more electrons. except by small changes in the outer (valance) electrons. surrounded by negatively charged electrons that orbit around the nucleus. or sulphate ions. crystals and other structures. and hence by the charge on the nucleus. and are known as anions (e. UMIST Module 0. Chemical and Electrochemical Reactions . you need to be aware of a number of terms that are used in chemistry. sodium ions. Element The chemical nature of an atom is determined by the number of electrons that orbit the nucleus.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. Bonds Chemistry is largely about the ways in which atoms can join together to form molecules. usually in an ionic crystal.g.Page 1 .2003. Ionic bonds are produced when anions and cations are held together by electrostatic forces. then we suggest that you look at the relevant sections in Corrosion. Na+. An element is a mass composed of atoms with all the same charge on the nucleus.

As a general rule homogenous reactions occur more easily than heterogeneous reaction. 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. because they can occur throughout the volume. As the charge carriers in a metal are electrons. and the number of atoms of the various elements will not change. Chemical reactions only involve changes in the bonding between the atoms that are involved. whereas free electrons cannot exist in solution (with a few rather rare exceptions. Module 0.Page 2 © 2002 . or ‘catalyse’ it. liquid or solid) are known as homogeneous reactions. but overall they will not involve a change in the number of electrons. rather than occurring only at the boundary. solid surfaces may assist in the reaction. while reactions occurring at the interface between two phases are known as heterogeneous reactions.+ 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. molecules or ions). electrochemical reactions may be thought of as reactions that produce or consume electrons. Types of chemical reaction Chemical reactions may be classified in a number of types. However. Chemical and Electrochemical Reactions . Reactions occurring within a single phase (gas.2003. such as liquid ammonia).Chemical reactions Chemical reactions occur when one or more reactants (which may be atoms. gases or other solids. Chemical reactions may involve a transfer of electrons from one species to another. Chemical reactions may occur between species dissolved in a liquid (including the liquid itself) in a gas mixture. combine to produce one or more products. UMIST . between components of a ‘solid solution’ or at the interface between solids and liquids. and some of the common reaction types are summarized in Table 1.

For chemical reactions we must also have the same net charge on each side of the equation. ‘Balancing a chemical reaction’ is the process of adjusting the numbers of each molecule. Table 2 – Example electrochemical reactions Type of Reaction Examples Anodic Fe → Fe2+ + 2e- Zn → Zn2+ + 2e- Fe2+ → Fe3+ + e- 4OH. To take and example. Reactions that consume electrons result in the reduction of the species in solution. and there is no change in the chemical species present. d = 4. so we know that it consumes electrons.= dOH- Balancing the reaction then involves the determination of a. this is also true for electrochemical reactions. so we can write the reaction as: aO2 + bH2O + c e. and are know as cathodic reactions. → O2 + 2H2O + 4e- Cathodic O2 + 2H2O + 4e. Consequently. → H2 + 2OH- Fe3+ + e. c = 4. UMIST Module 0. 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. and we remember that the reaction produces hydroxyl ions.Page 3 . b and c such the numbers of oxygen and hydrogen atoms are the same on each side of the reaction.= 4OH- © 2002 . Examples of anodic and cathodic reactions are given in Table 2. → 4OH- 2H2O + 2e. we may remember that a common cathodic electrochemical reaction is the reduction of dissolved oxygen. → Fe2+ Note that for every anodic reaction there is a cathodic reaction that is the reverse (see the two examples in Table 2). we must have the same number of atoms of each species on each side of the equation. leading to: O2 + 2H2O + 4e. Balancing Reactions Chemical and electrochemical reactions involve changes in the bonding of atoms. Chemical and Electrochemical Reactions . b = 2. atom and ion on each side of a reaction such that the above requirements are met. and that the net charges are the same. but we normally aim for the smallest solution for which all the numbers are integers. in this case a = 1.Reactions that produce electrons result in the oxidation of the species in solution and are known as anodic reactions. This is an electrochemical reaction.2003. molecules or ions. providing we include electrons in the calculation of the charge. when we write the equation for a chemical reaction.

2. Work out which species are likely to be present on each side of the equation. so you can shift it to a positive number on the other side. Chemical and Electrochemical Reactions .Page 4 © 2002 . UMIST .Some authors will permit fractional values.2003. It may involve some guesswork or trial and error to decide where to place species such as water. but it doesn’t 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. Module 0.= 2OH- Then the general approach to constructing and balancing a chemical equation is: 1. 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. so this reaction may also be written as: ½O2 + H2O + 2e.

UMIST Module 0.© 2002 .Page 5 . Chemical and Electrochemical Reactions .2003.