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Helen Jacobs

Novelette Sadler-McKnight Stewart McLean


Patrice Piggot-Cumberbatch
Graeme Corbin Mike Taylor

CHEMISTRY®
FOR CAPE EXAMINATIONS
Chemistry
For CAPE® Examinations
The Higgs boson
In the early 19th century atoms were thought to be the ultimate, indivisible, components of
matter. Then came the discovery of the atomic nucleus, made up of protons and neutrons,
and the electrons that surround the nucleus. We now know that electrons are indeed
indivisible, but that protons and neutrons are themselves made up of ‘quarks’: it takes three
quarks to make either a proton or a neutron.
We have also learned that matter and energy are one and the same thing, according to
Einstein’s famous equation E = mc2. But this is a concept outside our everyday experience,
which we can accept and use but not picture happening.
Another such concept is the idea of ‘action at a distance’. Two magnets attract or repel
one another, but why and how do they do this? We get round it by saying that there is
a magnetic ‘field’ between them, with ‘lines of force’ that change shape and produce the
attractive or repulsive effect. But is that really an explanation?
Today’s explanation (called the standard model) says that there is a region of space round
the magnets (the ‘field’) inside which the magnets throw other particles to and fro between each
other. It is like children who throw and catch a ball: as long as they do so, they stay together.
If the ball is very heavy the thrower staggers backwards after throwing and so does the
catcher. It is the exchange of energy packets which is the ‘force’.
There are only four forces in nature. These are gravity, electromagnetism, the ‘strong force’
(which holds nuclear particles together) and the ‘weak force’ (responsible for effects such as
magnetism). Each one comprises a field and an associated exchange particle.
But there is a problem with the standard model. Nothing in it makes possible the property
that we call mass. It was this problem which led Professor Higgs and his co-workers to
suggest that the whole universe is filled with a ‘mass field’ and that particles interact with
that field to acquire ‘mass’. If that is the case, the mass field, like any other, must have an
exchange particle associated with it. Some very subtle physics showed that the particle must
have a particular property; it must behave as though it had no spin. Such a particle-cum-
energy-packet is called a boson. The exchange particle which goes with the mass field is
called the Higgs boson.
Other calculations showed that such a particle could only exist for, at most, nanoseconds
and that it would carry (or be) a large amount of energy. The only way to find it would be
to smash two other particles together at speeds near to that of the speed of light. For this
you need the apparatus called the Large Hadron Collider (LHC). It was in the LHC on July
4th 2012 that collisions were seen which could only have come from the decay of a Higgs
boson. The tracks that you see in the cover picture of this book (a computer visualization of
the response of the huge array of detectors in the LHC) are some that can only have come
from the decay of the Higgs boson. Any other particle could not produce exactly these traces
as it decayed.
Chapter 1 Atomic structure III

Chemistry ®
For CAPE Examinations
Helen Jacobs, Novelette McKnight, Stewart
McLean, Patrice Piggot-Cumberbatch,
Graeme Corbin, Mike Taylor

CAPE® is a registered trade mark of the Caribbean


Examinations Council (CXC).
Chemistry For CAPE® Examinations is an independent
publication and has not been authorized, sponsored,
or otherwise approved by CXC.
Macmillan Education
4 Crinan Street, London N1 9XW

A division of Macmillan Publishers Limited


Companies and representatives throughout the world

ISBN 978-0-230-48315-6 AER

Text © Helen Jacobs, Novelette McKnight, Stewart McLean,


Patrice Piggott-Cumberbatch and Mike Taylor
SBA chapter contributed by Graeme Corbin and © Macmillan
Publishers Limited.
Design and illustration © Macmillan Publishers Limited 2014

First published 2014

All rights reserved; no part of this publication may be reproduced,


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Cover design by Clare Webber and Macmillan Education
Cover photograph by Pasieka, Science Photo Library

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Contents
Preface Chapter 4 Chemical bonding 33
Introduction 33
UNIT 1 Formation of bonds 33
Chemical principles and applications I Types of chemical bond 33
Bond formation and energy changes 34
Module 1 Ionic bonding 35
Fundamentals in chemistry Covalent bonding 35
Chapter 1 Atomic structure 2 The hydrogen bond 37
The atom: introduction 2 The metallic bond 38
Early ideas about the atom: classical models 2 van der Waals forces 39
Atomic structure 4 The periodic table and bond type 40
Electrons in atoms 7 Properties associated with different bond types 40
Summary 10 Mixed bonds 41
Review questions 10 Summary 42
Answers to ITQs 10 Review questions 42
Answers to Review questions 11 Answers to ITQs 42

Chapter 2 The quantum atom and the periodic table 12 Chapter 5 Shapes of covalent molecules 43
The quantum atom 12 Lewis structures 43
Developing the periodic table 16 Molecular geometry 44
The modern periodic table 17 Hybrid orbitals 47
Periodicity 18 Resonance 48
Periodic properties in atomic ‘size’ 18 Molecular polarity 49
Summary of general periodic trends 24 Two common misconceptions 50
Summary 25 Summary 51
Review questions 25 Review questions 51
Answers to ITQs 26 Answers to ITQs 52
Answers to Review questions 27 Answers to Review questions 52

Chapter 3 Radioactivity 28 Chapter 6 An introduction to the mole 53


Introduction: the alchemists’ dream 28 Relative atomic mass of elements, Ar 53
Nuclear transitions 29 Relative formula mass and relative molecular
Radioactive decay 30 mass of compounds 53

Properties of α, β and γ rays 30 The mole 54

Problems caused by radiation 30 Molar mass 54

Uses of radioisotopes 31 Writing chemical equations 55

Summary 32 Calculations involving the mole 56

Review questions 32 The concept of the limiting reagent 57

Answers to ITQs 32 Empirical and molecular formulae 59


The mole concept applied to solutions 61
Titrimetric (volumetric) analysis 63
The mole concept applied to gases 64
Summary 66
Review questions 66
Answers to ITQs 67
Answers to Review questions 67
VI Contents

Chapter 7 Gases 68 Chapter 11 Acid/base equilibria 104


Behaviour of gases 68 What are acids and bases? 104
Gas laws 69 Acid/base reactions 104
Behaviour of real gases 71 Strong and weak acids and bases 105
Kinetic-molecular theory 72 pKa 105
Summary 72 pH 105
Review questions 73 Changes in pH in acid/base titrations 106
Answers to Review questions 73 Buffer solutions 107
Solubility product 108
Chapter 8 Thermochemistry 74
Summary 110
Introduction to thermodynamics 74
Review questions 110
Heat and heat capacity 75
Answers to ITQs 110
Latent heat 76
Answers to Review questions 111
Heat and the kinetic-molecular theory 77
Heat and work 77 Chapter 12 Redox equilibria 112
The first law of thermodynamics 78 Introduction 112
Calorimetry 79 Electrode potential 113
Enthalpy 80 Galvanic cells: using redox reactions to
Summary 86 generate electricity 113
Review questions 87 The standard hydrogen electrode (S.H.E.) 114
Answers to ITQs 87 Measuring standard electrode potentials 115
Answers to Review questions 87 Measuring the E of half-cells involving
non-metals 116
Module 2 Uses of standard electrode potentials 116
Kinetics and equilibria The effect of concentration on electrode
potential 119
Chapter 9 Chemical kinetics 88 Energy storage devices 119
Collision theory 88 Summary 123
Reaction rate 89 Review questions 123
Determining the order of reaction 93 Answers to ITQs 125
Summary 95 Answers to Review questions 125
Review questions 95
Answers to ITQs 97 Module 3
Answers to Review questions 97 Chemistry of the elements
Chapter 10 Chemical equilibrium 98 Chapter 13 Elements and periodicity: period 3 126
Reversible reactions 98 Introduction 126
Gas reactions 99 Atomic properties 126
Le Chatelier’s principle 100 Bulk properties 129
Changes in the value of K 101 Chemical properties 131
Summary 102 Summary 133
Review questions 102 Review questions 134
Answers to ITQs 103 Answers to ITQs 135
Contents VII

Chapter 14 Elements and periodicity: Group II 136 UNIT 2


Introducing Group II 136
Chemical principles and applications II
Physical properties 136
Chemical reactions 137 Module 1
Uses of magnesium and calcium compounds 139 The chemistry of carbon compounds
Summary 142
Chapter 19 Alkanes 182
Review questions 142
Introduction to carbon compounds 182
Answers to ITQs 143
Alkanes 185
Answers to Review questions 143
Physical properties, sources and uses
Chapter 15 Elements and periodicity: Group IV 144 of alkanes 188
Introducing Group IV 144 Reactions of alkanes: an introduction 189
Variation in physical properties 144 Summary 191
The Group IV tetrachlorides 145 Review questions 192
The Group IV oxides 146 Answers to ITQs 192
Bonding and the ‘inert pair’ effect 147 Chapter 20 Alkenes and alkynes 193
Stability of the +2 and +4 oxidation states 147 Introduction 193
Silicon 148 Alkenes 193
Summary 149 Alkynes 195
Review questions 150 Physical properties, sources and uses
Answers to ITQs 151 of alkenes and alkynes 196
An introduction to the reactions of alkenes
Chapter 16 Elements and periodicity: Group VII 152 and alkynes 196
Introducing the Group VII elements 152 Summary 198
Variation in physical properties 152 Review questions 198
Bonding types 153 Answers to ITQs 199
Chemical properties and reactivity 153
Summary 157 Chapter 21 Alcohols and amines 200
Review questions 158 Introduction 200
Answers to ITQs 159 Haloalkanes 200
Alcohols 200
Chapter 17 The first row transition elements 160 Amines – RNH2 205
Introduction to the transition elements 160 Summary 208
Electronic configurations 160 Review questions 208
Trends across the period of transition elements 161 Answers to ITQs 209
Characteristic properties 162
The oxidation states of vanadium 169 Chapter 22 Stereochemistry 210
Summary 170 Introduction 210
Review questions 171 Structural isomers 210
Answers to ITQs 172 Geometric isomers 210
Answers to Review questions 172 Summary 214
Review questions 214
Chapter 18 Qualitative inorganic analysis 173 Answers to ITQs 214
Introducing inorganic analysis 173
Identification of cations 173
Flame tests 174
Identification of anions 175
Testing for gases 177
Review questions 179
Answers to ITQs 180
Answers to Review questions 180
VIII Contents

Chapter 23 Aldehydes and ketones 215 Chapter 27 Reaction mechanisms 258


Introduction 215 Introduction 258
Nomenclature of aldehydes and ketones 216 Homolytic and heterolytic cleavage 258
Bonding in the carbonyl group 216 Homolysis and radical reactions 259
General properties of aldehydes and ketones 217 Heterolysis and ionic reactions 261
Preparation of aldehydes and ketones 218 Nucleophilic substitution reactions 263
Reactions of aldehydes and ketones 218 Summary 265
Summary 222 Review questions 265
Review questions 222 Answers to ITQs 266
Answers to ITQs 222
Module 2
Chapter 24 Carboxylic acids and derivatives 224 Analytical methods and separation techniques
Introduction 224
Nomenclature 224 Chapter 28 Measurement in chemical analysis 268
General properties 224 Introduction 268
Preparation of carboxylic acids 225 Defining some terms 268
Acidity of carboxylic acids 225 Uncertainty in single determinations 269
Amino acids 226 Uncertainty in addition and subtraction 270
Reactions of carboxylic acids and their Significant figures 271
derivatives 228 Glassware used for measuring volume 271
Summary 232 Measuring mass 272
Review questions 232 Summary 273
Answers to ITQs 233 Review questions 273
Answers to ITQs 273
Chapter 25 Aromatic compounds 234
Introduction 234 Chapter 29 Gravimetric analysis 274
Characteristics of aromatic compounds 235 Introduction 274
The stability of benzene 235 The precipitation method 274
The electron structure of benzene 236 Apparatus and glassware for gravimetric
Aromaticity 236 analysis 275
Nomenclature of benzene derivatives 237 Volatilization methods 276
Properties and uses of aromatic compounds 237 Applications of gravimetric analysis 278
Reactions of benzene 238 Summary 279
Properties and reactions of aniline 240 Review questions 279
Properties and reactions of phenol 241 Answers to ITQs 280
Summary 243 Chapter 30 Titrimetric analysis 281
Review questions 243 Introduction 281
Answers to ITQs 244 Acid/base titrations 281
Chapter 26 Macromolecules 245 Back titrations in acid/base titrimetric analysis 284
Introduction 245 Titrations monitored by measurement of pH
(potentiometric titrations) 286
Polymerization 245
Thermometric and conductimetric titrations 287
Addition polymerization 245
Primary standards 287
Condensation polymerization 248
Redox titrations 287
Carbohydrates 251
Summary 294
Plastics in the environment 253
Review questions 295
Waste management 254
Answers to ITQs 295
Summary 255
Review questions 256
Answers to ITQs 257
Contents IX

Chapter 31 Introduction to spectroscopy 296 Chapter 35 Phase separations 322


Introduction to spectroscopy: resonance 296 Introduction 322
Electromagnetic radiation 297 Simple distillation 322
Regions of the electromagnetic spectrum 298 Fractional distillation 323
The interaction of electromagnetic radiation Vacuum distillation 327
with atoms and molecules 298 Steam distillation 327
Effects of irradiation 299 Solvent extraction 328
Summary 300 Summary 330
Review questions 300 Review questions 331
Answers to ITQs 300 Answers to ITQs 333
Chapter 32 Ultraviolet–visible spectroscopy 301 Chapter 36 Chromatography 334
Molecular orbitals in covalent molecules 301 Introduction 334
Absorption of energy by electrons in molecular Chromatography 334
orbitals 302
Elution 334
Studying absorption of UV–visible radiation 303
Locating individual substances 335
The Beer–Lambert law 304
Ion-exchange chromatography 336
Applications of ultraviolet–visible spectroscopy 304
Identifying peaks in a chromatogram 336
Summary 306
Uses of chromatography 337
Review questions 307
Gas-liquid chromatography 337
Answers to ITQs 307
Summary 338
Chapter 33 Infrared spectroscopy 308 Review questions 338
Introduction 308 Answers to ITQs 338
How organic molecules absorb infrared
radiation 308 Module 3
Interpreting infrared spectra 309 Industry and the environment
Obtaining infrared spectra 311
Chapter 37 Environmental effects 339
Infrared absorption in climate and the
Locating industrial plants 339
environment 312
Water 341
Summary 312
The atmosphere 346
Review questions 313
Solid waste 356
Answers to ITQs 313
Answers to ITQs 362
Chapter 34 Mass spectrometry 314
Chapter 38 Chemical industry 364
Introduction 314
Aluminium 364
Mass spectra of atoms 314
Crude oil 366
Mass spectra of molecules 315
Ammonia 372
How mass spectra are obtained 316
Ethanol 374
Applications of mass spectrometry 316
Chlorine 378
Summary 320
Sulfuric acid 381
Review questions 320
Answers to ITQs 384
Answers to ITQs 321

CAPE SBA 385


Index 399
X

Preface

This series of textbooks for CAPE Sciences follows directly from


Macmillan’s CSEC Science series. The books in the series will be
especially valuable for students who have completed CSEC Science
examinations successfully, and wish to continue their studies at a higher
level, to gain employment in a scientific field or to extend their education
at degree level.
CAPE subject studies are each divided into two units, and students have
the option to study either or both of them. These books are designed
to be used with any of these three options. In each unit the material is
based on the knowledge and skills that the student will have gained in
CSEC studies.
The move to higher-level studies is not without its pitfalls. To minimize
these problems the books have several new and innovative features.
In the sciences a good diagram is worth a thousand words. Diagrams
in these books are carefully presented to convey the maximum
understanding with the minimum of extraneous detail. Their captions
are comprehensive, to help the reader to integrate the visual material as
fully and easily as possible with the text.
As in the familiar CSEC series, use is made of ‘In-text Questions’ (ITQ),
but at this level they provoke analytical thought rather than confirm
comprehension.
All science teachers are aware of fundamental misconceptions that are
commonly held. Throughout these books, notes are provided to highlight
and dispel these misapprehensions.

Dr Mike Taylor
Adviser
Chapter 1 Atomic structure 1

Unit 1
Chemical principles and applications I
2

Module 1
Fundamentals in chemistry

Chapter 1
Atomic structure
Learning objectives
■ Compare the properties of electrons, protons and neutrons in terms of their relative charges, masses
and behaviour in electric and magnetic fields.
■ Distinguish between atomic number and mass number.
■ Discuss the concept of isotopes and give examples.
■ Summarize Dalton’s, Thomson’s and Rutherford’s models of the atom.
■ Outline the Bohr theory and model of the atom and explain how it accounted for the absorption and
emission spectra of hydrogen.
■ Perform calculations using energy, wavelength and frequency of electromagnetic radiation, using E = hv.
■ State and explain the origins of the Lyman, Balmer and Paschen series in the hydrogen spectrum.

The atom: introduction Early ideas about the atom: classical


The study of the atom is at the core of chemistry. By
models
studying the atom we gain a greater understanding of the The Ancient Greek and Roman philosophers debated about
physical, chemical and structural properties of compounds. the composition of matter. Some, for example Plato and
The concept of the atom has undergone many changes, Aristotle, argued that matter was continuous. Others,
from the early ideas of it being indivisible, as proposed by for example Democritus, believed that matter could be
the Greeks, to the modern quantum mechanical model in divided in such a way that an ultimate particle could be
which it behaves both as a particle and as a wave. The atom, attained beyond which any further sub-division would be
which was once thought to be hollow on the inside, has now, impossible. Democritus (460–370 BCE) named this ultimate
through experiments, been shown to contain electrons, particle atomos, the Greek word meaning ‘indivisible’. This
protons and neutrons, with these particles being formed concept of an ultimate particle was maintained for about
of other sub-atomic particles. With the use of sophisticated 2000 years without any scientific experiments being
instruments, for example a scanning tunnelling microscope, conducted to prove or disprove it. This approach to science
images of individual atoms have been produced. changed in the eighteenth century, as chemists began to
make measurements of the changes in mass and volume
In this chapter we will review the classical models proposed
that could be observed.
to explain the structure of the atom. Chapter 2 goes on to
look at the quantum mechanical model of the atom. The
Early quantitative ideas
development of these models is an excellent example of
how scientists (chemists, physicists, mathematicians) work The works of Joseph Priestley, an English theologian and
together as a team to design and conduct experiments, to chemist (1733–1804), and Antoine Lavoiser, a French
test hypotheses and develop or refute models and theories. nobleman and chemist (1743–1794), centred on the
As experimental evidence becomes available, existing process of combustion. Their work led to the development
models are confirmed, modified or abandoned. of two key fundamental principles of chemistry: the
Chapter 1 Atomic structure 3

law of conservation of mass and the law of definite other atoms. Since hydrogen was the lightest (least dense)
proportions. element known at the time, he assigned it an ‘atomic
The law of mass conservation states that mass is neither weight’ of 1. The theory was tested by other investigators
created nor destroyed during a chemical reaction. in their attempts to determine the relative atomic masses of
elements from their mass ratios in compounds.
This means that the combined masses of the products of a
reaction are always equal to the combined masses of the Chemists thought that water consisted of roughly 15%
starting reactants. hydrogen and 85% oxygen by mass. Dalton assumed that
atoms combined in the simplest ratios. As a result, he gave
The law of definite proportions states that different samples water the formula HO, and calculated that oxygen had an
of a pure substance always contain the same proportions of atomic weight of 5.7.
the same elements by mass.
These results were challenged by Joseph Gay-Lussac, a
This statement codifies the idea of a ‘pure’ substance. For French chemist (1778–1850). He, like Dalton, conducted
example, every sample of water, regardless of its origin, experiments with gases. Instead of measuring the mass
will contain eight parts of oxygen to one part of hydrogen of the gasses, Gay-Lussac used their volumes. When he
by mass. combined hydrogen gas and oxygen gas to form water
vapour, he observed that:
Dalton’s theory
■ 2 dm3 of hydrogen gas combined with 1 dm3 of oxygen
In the early 1800s, John Dalton, an English schoolteacher
gas;
and chemist (1766–1844), proposed a new atomic theory.
■ 2 dm3 of water vapour was formed for every 2 dm3 of
Unlike the ideas proposed by the Greeks, Dalton’s work
hydrogen gas that reacted;
consisted of statements about the atom that could be
■ 2 dm3 hydrogen gas + 1 dm3 oxygen gas →
tested through experiments. He carried out experiments
2 dm3 water vapour.
in which he combined elements in different ratios to form
compounds. He noticed that certain patterns resulted. For At that time all elements were thought to be composed of
example, when he combined hydrogen with oxygen to single atoms. Many thought that equal volumes of gases
form water, the ratio of the mass of oxygen to the mass of contained equal numbers of particles. Dalton used symbols
hydrogen was 8:1, whereas in hydrogen peroxide, the ratio for atoms and would have suggested this equation:
of the mass of oxygen to the mass of hydrogen was 16:1.
+ =
On the basis of these and other experiments, he proposed
H + O = HO
the following:
1 vol 1 vol should give1 vol
■ all matter is composed of tiny indestructible particles
However, Gay-Lussac’s results suggested that water is
called atoms that cannot be created, destroyed or
H2O, and not OH as was suggested from Dalton’s theory.
subdivided;
Problems like these caused confusion amongst chemists for
■ atoms of one element cannot be converted into atoms
some years.
of another element;
■ all atoms of a given element are identical, in weight In 1811 Amadeo Avogadro, an Italian physicist (1776–
and other properties, and are different from atoms of 1856), suggested that individual elements could exist as
any other elements (nowadays we would say ‘mass’, ‘molecules’, such as O2, rather than as single atoms. For
not ‘weight’); example, a hydrogen gas ‘particle’ consisted of two atoms
■ atoms can combine with each other in simple whole
that could split apart to form two separate atoms. The same
number ratios. is true for each oxygen ‘particle’. The separate atoms of
hydrogen and oxygen then recombine to form molecules
Dalton’s theory incorporated the idea of an indestructible
of water vapour.
atom, suggested by Democritus, as well as the law of
conservation of mass and the law of definite proportions,
+ =
proposed earlier by Lavoisier and Priestley.
According to Dalton’s theory, the small size of an individual 2H2 + O2 = 2H2O
2 vol 1 vol 2 vol
atom makes it impossible for us to determine its mass
directly so its mass must be measured relative to the mass of
4 Unit 1 Module 1 Fundamentals in chemistry

Avogadro’s suggestion fitted exactly with Gay-Lussac’s electric current was passed through them. Based on this, he
result. This idea was eventually accepted and we now have proposed the existence of ‘an electromotive force’ holding
no problem with the idea of elemental molecules. Later, elements together in chemical compounds.
Avogadro’s ideas were used to confirm the relative atomic In 1832 Davy’s student, Michael Faraday (1791–1867),
mass of oxygen as 16 and to unify a system of ‘atomic established that the amount of substance produced by a
weights’ on which all chemists could agree. chemical reaction during electrolysis is proportional to the
Chemists had begun to realize that atoms might have a quantity of electricity that passed through the electrolysis
more complex structure than that of a solid ball that Dalton cell.
had suggested. In the late 1860s, Sir William Crookes, an English physicist
(1832–1919), designed experiments in which he passed
Limitations of Dalton’s theory an electric current through sealed evacuated tubes. These
Dalton’s theory could not explain the following: tubes contained metals as both the positive and negative
■ why elements combined in the specific ratios observed; electrodes, connected to an external source of electricity.
■ the electrical nature of particles, which were being
He observed ‘rays’ that travelled in a straight line from
observed in other experiments. the negative electrode (cathode) to the positive electrode
(anode), regardless of the metal used as the cathode. He
As an example, in 1807 Humphry Davy, an English chemist named these ‘cathode rays’. His conclusion was ‘that
(1778–1829), had connected a sample of ‘potash’ (what we cathode rays are negatively charged’.
would now call soluble potassium compounds) between
screen cathode
the plates of a battery and observed a ‘vivid action’ taking
place. Dalton’s theory didn’t explain why electricity would
have such an effect.
Table 1.1 Dalton’s theory and its limitations
Dalton’s theory What is now known
Matter consists of tiny indivisible particles Atoms are not indivisible and are
(atoms) that cannot be created or composed of sub-atomic particles. + –
destroyed. battery
Atoms of one element cannot be During a chemical reaction this idea
converted into atoms of another element. is true. However, in nuclear reactions Figure 1.1 Crookes’ tube, showing the shadow image caused by
During a chemical reaction, reacting atoms of one element can change the cathode rays.
molecules separate into atoms that into atoms another element.
recombine to form different molecules.
Other scientists found that the rays cast sharp-edged
Atoms of a given element are identical Atoms of an element can have
in mass and other properties and are slight differences in their mass and shadows, as shown in Figure 1.1. In 1869, Johann Hittorf, a
different from atoms of any another properties. Isotopes will be discussed German physicist (1824–1914), recognized that this could
element. later in this chapter.
be explained if the ‘rays’ were in fact a stream of particles.
Atoms of different elements combine True for most compounds, but there
with each other in simple specific whole are a few compounds in which there In 1897, John Joseph Thomson, an English physicist
number ratios to give combined atoms are slight variations in their atomic
(molecules). This is the law of multiple ratios.
(1856–1940), investigated these rays further and found
proportions. that they could be deflected by electric and magnetic fields.
He showed that they were made up of very light particles.
Atomic structure The results of his experiments enabled him to calculate
their ratio of charge to mass (e/m). He found this to be
Discovery of the electron 1.8 × 1011 C kg−1. The accurate value that we now use is
Although Dalton’s ideas were only partly correct, they e/m = 1.759 × 1011 C kg−1. Thomson further estimated that
could be tested experimentally. They paved the way for the mass of the electron was approximately 1/1840 that of
the development of more ideas and theories. This process the mass of one atom of the lightest element, hydrogen.
of one theory suggesting new ideas and new theories The observation of cathode rays coming from atoms
suggesting further experiments is how science develops. contradicted Dalton’s theory that atoms are indivisible and
As mentioned above, in the early 1800s Humphry Davy suggested that all atoms contained these negatively charged
observed that some substances were decomposed when an particles of extremely tiny mass. The particles came to be
called ‘electrons’.
Chapter 1 Atomic structure 5

Thomson concluded that since matter as a whole is further used radioactivity as a tool to study the structure of
electrically neutral, the atom could be broken down into matter. In one experiment he and his research students,
two parts; one negatively charged and the other positively Hans Geiger and Ernest Marsden, designed and carried out
charged. The negatively charged parts (electrons) were experiments in which a very thin gold foil was bombarded
observed to be easily removed from the atom but the with alpha particles. (Alpha particles are positively charged
positively charged parts were not. helium nuclei – see Chapter 3, page 29.)
In 1904, Thomson proposed that the atom was ‘jelly-like’, They observed that:
consisting mainly of positive charge distributed throughout ■ most of the particles passed through the gold foil with
the jelly with electrons embedded in this jelly rather little or no deflection;
like plums in a pudding. This model is called the ‘plum
■ a few particles were deflected off course slightly;
pudding’ model (Figure 1.2). The negative charges balance
■ a very few particles were deflected backwards, almost
the positive charges so the atom is electrically neutral.
in the direction from which they came (Figure 1.3).
Thomson therefore provided the experimental evidence
that the atom did posses an internal structure, directly electrons nucleus
against Dalton’s model of the indivisible atom. The radius
of an atom based on this model was 10−10 m. alpha
particles

atom

Figure 1.3 A representation of Rutherford’s gold foil experiment,


showing the deflection observed when a beam of alpha particles
hit a metal target.

These results were quite stunning and totally unexpected.


Figure 1.2 Thompson’s plum pudding model. The electrons are Rutherford’s recollection of the results is worth quoting:
the ‘plums’ mixed throughout the positively charged ‘pudding’.
‘It was quite the most incredible event that has ever happened to
Thomson’s conclusions were that: me in my life. It was almost as incredible as if you fired a 15-inch
shell at a piece of tissue paper and it came back and hit you.’
■ all matter is made up of negatively charged particles
‘enclosed in a sphere of uniform positive electrification’; If Thomson’s plum pudding model of the atom was true,
■ the negative particles contribute only a tiny fraction of
then all the positively charged alpha particles should pass
the mass of the atom. through the jelly-like diffuse positive charges with only
slight, occasional deflections. Rutherford and his team
Rutherford and the nuclear atom concluded that since most of the alpha particles passed
Ernest Rutherford, a New Zealand-born British chemist through the gold foil without being deflected, then an atom
(1871–1937) was working with radioactive materials. He is comprised of mainly empty space in which the electrons
was building on the earlier discoveries of X-rays by Wilhelm are located. The few positively charged alpha particles that
Roentgen in 1895 and radioactivity by Henri Becquerel in were deflected backwards in the direction from which they
1896 (work then developed by Marie and Pierre Curie). came, resulted from the repulsion by a positive charge
In 1899, Rutherford proposed that there are three major concentrated in a tiny volume, much smaller than the
types of spontaneous radioactivity: alpha particles (α), atom itself.
beta particles (β) and gamma rays (γ). These particles/ Rutherford’s recollection continues:
rays display distinctly different properties when subjected
‘On consideration, I realized that this scattering backward must be
to electric and magnetic fields. Alpha particles and beta
the result of a single collision, and when I made calculations I saw
particles bend in opposite directions in an electric field
that it was impossible to get anything of that order of magnitude
while gamma radiation is unaffected by an electric field.
unless you took a system in which the greater part of the mass of
Alpha particles are positively charged helium nuclei, while
the atom was concentrated in a minute nucleus. It was then that I
beta particles are negatively charged high speed electrons
had the idea of an atom with a minute massive centre, carrying a
and gamma rays are uncharged (see Chapter 3). Rutherford
charge.’
6 Unit 1 Module 1 Fundamentals in chemistry

Rutherford’s experiment suggested that the positive charge has an atomic number that is unique to it. Each atom of a
of the atom is essentially concentrated in a ‘nucleus’ (from given element has the same atomic number. For example,
the Latin nucleum meaning ‘kernel’) that was extremely all nitrogen atoms have an atomic number of 7 since they
small (the diameter of the nucleus was estimated to be each have seven protons. If they didn’t have seven protons
≈10−15 m) and therefore very dense. Surrounding the then they wouldn’t be nitrogen atoms.
nucleus was mainly empty space containing the electrons. The mass number of an atom is the total number of its
In this model of the atom the positively charged nucleus protons and neutrons. The mass of the electron is not
was at the centre, with the electrons revolving around the included since its mass is only 1/1837 of a mass unit
nucleus in a manner similar to the Sun and the planets, whereas each proton has a relative mass of 1 unit and each
with most of the mass of the atom being in the nucleus. neutron also has a relative mass of 1 unit. A nitrogen atom,
The positive charges in the nucleus are exactly balanced for example, that has seven protons and seven neutrons
by the negative charges on the surrounding electrons, will have a mass number of (7 + 7) =14.
resulting in the atom being electrically neutral. In the shorthand atomic symbol of an element, the mass
The number of positive charges in the nucleus of an atom number is written on the left as a superscript and the atomic
is called the atomic number (Z). This value is different number on the left as a subscript. For example, the isotope
for each element and is characteristic of it. The positive of uranium used in nuclear reactors can be symbolized as
238
nucleus of the hydrogen atom was called a proton (from 92 U.

the Greek word proton meaning ‘first’). The number of neutrons can be found by subtracting the
Rutherford speculated about structure of the nucleus, atom’s atomic number from the mass number. The example
suggesting in 1920 that another particle was involved. above represents an atom with 92 protons (uranium),
When alpha particles (helium nuclei) were used to while the protons and neutrons total 238. Therefore the
bombard elements such as beryllium, an intensely atom contains 146 neutrons.
penetrating radiation was emitted. At first it was thought number of neutrons = mass number − atomic number
that this was gamma radiation (see Chapter 3, page 30), =A−Z
but then it was realized that it consisted of neutral particles
with a mass only slightly greater than that of the proton. Isotopes of elements
Finally, in 1932, James Chadwick, an English physicist
One of John Dalton’s ideas was that ‘all the atoms of a
(1891–1974), discovered the third sub-atomic particle.
particular element are identical in weight’. This is only
Because the particles were electrically neutral they were
partly true. The factor that fixes the identity of an element
called ‘neutrons’.
is the number of protons in its nucleus (Z). However, the
Sub-atomic particles nucleus also contains neutrons; the neutrons contribute
mass but have almost no effect on chemical properties.
Atoms were therefore shown to be made up of smaller Therefore, it is possible to have atoms of an element,
particles, with properties summarized in Table 1.2. all with the same number of protons, but with different
Table 1.2 Sub-atomic particles numbers of neutrons and, hence, different masses. These
Name and Charge Mass Location variants are called isotopes of the element.
symbol
1 Isotopes of an element have same number of protons
relative: −1 relative: 1837 outside
electron, e− (atomic number, Z) but different number of neutrons and
absolute: −1.602 × 10−19 C nucleus
absolute: 9.109 × 10−28 g therefore different mass numbers (A).
relative: +1 relative: 1 inside
proton, p+
absolute: +1.602 × 10−19 C absolute: 1.673 × 10−24 g nucleus
relative: 0 relative: 1 inside
Relative atomic mass and isotopic mass
neutron, n0
absolute: 0 absolute: 1.675 × 10−24 g nucleus Chemists in the nineteenth century referred to the ‘atomic
The atomic number of an element (Z) is equal to the weight’ of an element. What they were really talking about
number of protons in the nucleus of its atoms. Each element was the ‘relative atomic weight’, taking the weight of a

ITQ 1 Carbon has three naturally occurring isotopes, 12C, 13C and ITQ 2 The relative atomic masses of most elements are not whole
14C. Work out the number of protons, electrons and neutrons in numbers. Why is this so?
each isotope of carbon.
Chapter 1 Atomic structure 7

hydrogen atom as 1. Today we refer to the relative atomic


mass (RAM) of an element. We use as our benchmark
atom the isotope 12C, which is taken as having a value of
12. This is a relative value (one mass divided by another),
so RAM has no units.
The relative atomic mass (RAM) of an element is the mass
1
of one atom of the element relative to 12 the mass of one
atom of the carbon-12 isotope (12C).
Relative isotopic mass is the mass of an atom of a specific
isotope of the element relative to the mass of the standard
carbon-12 isotope.
Every element occurs naturally as a mixture of isotopes. The Figure 1.4 The Bohr planetary model of the atom.
relative atomic mass is therefore a weighted average of all
the stable relative isotopic masses, taking their abundance subjected to a high voltage, it gives off a pink light. When
into account. For example, chlorine occurs as a mixture of you look at that light with a spectroscope, you see that it
35Cl (roughly 75%) and 37Cl (roughly 25%). The weighted
is a mixture of coloured lines, not a continuous spectrum
average of chlorine’s RAM is: like a rainbow.
75 25 3550 Bohr suggested that it was possible for electrons to remain
× 35 + × 37 = = 35.5
100 100 100 stable in orbits around a nucleus provided that the electrons
had specific energies (Figure 1.4). He also suggested that an
Actual atomic mass atom jumping from one energy state to another would give
Actual atomic mass, as opposed to relative atomic mass, is off light of a specific colour. He suggested that the electrons
1
measured in atomic mass units (amu). One amu is 12 the were held to the nuclei both by gravitational and electric
mass of a neutral atom of 12C. The atomic mass unit (amu) (coulombic) forces. Spectroscopic evidence, the existence
has now been changed to the Dalton (Da), so one atom of of characteristic lines, showed that the energy levels were
carbon-12 has a mass of 12 Da. However, it is to be hoped the same in all hydrogen atoms. Bohr called these energy
that you realize the error in saying that any individual levels ‘stationary states’.
atom of chlorine has an atomic mass 35.5 Da!
Bohr’s model for the hydrogen atom was based on the
following assumptions:
Electrons in atoms
■ Electrons revolve around the nucleus in circular
Rutherford correctly placed the nucleus of an atom at stationary states called orbits.
its centre, but the placement of the electrons posed him ■ The energy of an electron in these stationary states
problems. Electrons could not be placed at a distance from (orbits) is dependent on the distance (r) of the orbit
the nucleus and also be stationary because the electrostatic from the nucleus.
attractive force of the positively charged nucleus would ■ Only specific electron orbits of certain radii and certain
pull them towards the nucleus. On the other hand, if energies are allowed. No orbits exist between these
the electrons were to move, then based on the laws of allowed orbits.
classical physics, they would continuously radiate energy ■ The absorption of light energy by an electron can result
and eventually collapse into the nucleus. The electron can in a transition from an orbit of lower energy to one
apparently, therefore, be neither stationary nor in motion. of higher energy if the frequency of the light energy
supplied corresponds exactly to the energy difference
The Bohr model between the orbits (ΔE).
The arrangement of electrons around the nucleus of the ΔE = (Ehigher − Elower) = h ν (the Bohr frequency
atom remained a great challenge for scientists for many condition)
years. This dilemma was resolved in 1913 by the Danish
physicist Niels Bohr (1885–1962). Bohr was aware that ITQ 3 Why should an electron in a Bohr orbit NOT be stable,
if hydrogen gas is enclosed in a tube at low pressure and according to classical physics?
8 Unit 1 Module 1 Fundamentals in chemistry

■ Similarly, a transition from an orbit of a higher energy the next energy level. Each Bohr orbit was referred to as
to one of lower energy will result in the emission a shell. (There is no interaction between electrons in each
of light where the frequency of the emitted light shell.)
is such that the energy emitted exactly equals the
energy difference between the energy levels of the Successes of the Bohr model
orbits (Figure 1.5). Einstein had showed that light The Bohr model allowed for the derivation of the Rydberg
rays (regarded until then purely as wave motion) can constant (see footnote), as well as the accurate calculation
behave as particles (photons) carrying fixed amounts of the wavelengths of experimentally observed lines in
of energy, and that the energy of a photon is related the electromagnetic absorption and emission spectra of
to its frequency by the expression E = hv, where h is a one-electron species such as hydrogen and hydrogen-like
constant and v is the frequency of the light. species.
n=3
The Bohr model predicted the radius of the n = 1 orbit of
the hydrogen atom as 5.3 × 10−11 m and the ionization
energy (the energy required to completely remove an
n=2 electron from an atom of hydrogen) as 2.18 × 10−18 J.
n=1
Both of these results were in excellent agreement with the
ΔE = hv experimentally determined values.
+ Ze
The idea that chemical properties are based on the
outermost electrons fits with the arrangement of elements
in the periodic table. The periodic table is discussed in
Chapter 2 (page 17).
The most stable energy level of an atom is the one with
Figure 1.5 The Bohr atom emitting a photon.
the lowest energy and is referred to as the ground state
Notice that the last of these assumptions is meant to explain of the atom. In the case of the hydrogen atom this state is
why the observed emission spectra contain sharp lines. the n = 1 energy level. The other energy states for which
Conversely, the sharp lines in emission spectra provide n > 1 are referred to as excited states. The electron in the
evidence that Bohr’s theory is at least partly correct. n = 1 energy state of the hydrogen atom can jump from the
Bohr also suggested that chemical properties of atoms were ground state to an excited state provided that the correct
based on the electrons in the outermost orbit. Bohr’s model amount of energy is supplied. Similarly, when the electron
received strong criticism from the scientific community, is in the n = 2 energy state it can jump to another excited
especially since he offered no explanation as to why these state. These energy states and the electron ‘jumps’ are
stationary states existed. Bohr’s model gained greater shown in Figure 1.6.
acceptance only after it stood up to several specially designed Each series in Figure 1.6 is named after its discoverer.
experiments (especially that of Franck and Hertz) and after
it turned out to form the basis of the revolutionary new
n=7
theory of quantum mechanics (see Chapter 2, page 12). n=6
n=5
Pfund
The Bohr model and many electron atoms series
n=4
Brackett n=5
The hydrogen atom contains only one electron, which series
n=4 n=3
greatly simplifies the situation. Bohr’s model of the Paschen
series
hydrogen atom was applied to atoms containing many n=3

electrons. According to Bohr, each orbit can accommodate n=2


Balmer
series
a certain maximum number of electrons. When that orbit n=2
is filled then the additional electrons occupy an orbit in

Lyman
series
■ The Rydberg constant occurs in an expression which Bohr used to n=1
n=1
predict the frequency of spectral lines emitted by excited hydrogen gas
but which had been known empirically since the late nineteenth century. Figure 1.6 The energy level changes in the Bohr hydrogen atom.
Chapter 1 Atomic structure 9

■ The Lyman series (discovered in 1906) has Beyond Bohr …


wavelengths in the ultraviolet (UV) spectrum, resulting
Bohr’s theory, like Dalton’s a century before, built a
from electrons dropping from higher energy levels into
foundation on which new knowledge and understanding
the n = 1 orbit.
could be based. The single-electron atom (hydrogen) could
■ The Balmer series (discovered in 1885) has
be fitted to the Bohr model with some precision. Multi-
wavelengths in the visible light spectrum, resulting
electron atoms were not so easy to deal with. The many
from electrons falling from higher energy levels into
interactions between the electrons in their ‘orbits’ were too
the n = 2 orbit.
complex. Bohr was reduced to suggesting that (by analogy
■ The Paschen series (discovered in 1908) has with the Sun and planets), orbits could be circular, or
wavelengths in the infrared spectrum, resulting from elliptical to various degrees, that the orbits rotated about
electrons falling from higher energy levels into the the nucleus, and that an orbit could contain more than one
n = 3 orbit. electron. These ideas are developed further in Chapter 2.
The energy difference between the lines in the series
decreases as the energy increases (or the wavelength
decreases). Eventually the lines become so close that they
form a continuous band called a continuum. This can
be seen towards the top of Figure 1.6. At this point and
beyond it is impossible to distinguish between the lines
and a convergence limit is said to be reached (Figure
1.7). At the convergence limit, the electron will no longer
experience the effect of the nuclear attraction. In other
words, it is ‘free’ from the influence of the nucleus and the
atom that has lost the electron has become ionized.
A(g) → A+(g) + e–

15 ionized continuum above 13.6 eV

n=3
discrete bound states
10 n=2
Energy (eV)

ground state
0 n=1

Figure 1.7 The convergence limit.

Limitations of the Bohr model


■ No explanation was provided by Bohr as to why the
electron absorbs or emits radiation when it moves
from one energy level to another.
■ The Bohr model did not predict accurately all the lines
in the spectra of multi-electron atoms.
■ It did not predict the intensity of the lines.
■ It assumed that an electron occupies a specific orbit at
a specific distance (radius) from the nucleus. This was
shown by Heisenberg to be incorrect.
■ It could not explain why the frequency of spectral lines
is changed by an external magnetic field.
10 Unit 1 Module 1 Fundamentals in chemistry

Review questions
Summary
1 Naturally occurring boron consists of two isotopes,
✓ Atoms have quantized energy levels. 10B (19.9%) with an atomic mass of 10.0129 Da and
11B (80.1%) with an atomic mass of 11.00931 Da.
✓ An electron can move from one energy level to Calculate the atomic mass of naturally occurring
another only if it absorbs or emits a photon of
boron.
energy equal to the difference in the energy of
the two energy levels. 2 Describe the contributions made by (a) Dalton,
(b) Thomson and (c) Rutherford to our understanding
✓ Each element has a unique line spectrum which of the structure of the atom.
results from the emission of photons of specific
energy (and hence of specific frequency) as its 3 Calculate the energy in joules of 1 mole of photons
electrons move from higher to lower energy with (a) a frequency of 2.6 × 10–14 Hz and (b) a
levels. wavelength of 546 nm.
4 Sodium vapour lamps have a characteristic yellow
✓ Bohr’s model is successful in explaining the
colour. Given that the wavelength is 589 nm, calculate
line spectrum of hydrogen and many other
the frequency of this light.
one-electron species but failed when applied
to the spectra of atoms with more than one 5 Complete the following table:
electron. Atomic Mass Number of Number of Number of
Symbol Charge
number number protons neutrons electrons
✓ An atom consists of a nucleus containing 15N

positively charged proton(s) and neutral 19 20 +1


neutron(s). 1 2 0
✓ The nucleus of the atom is surrounded by the 11 12 10
90
negatively charged electron(s). Sr2+

✓ The number of electrons is equal to the number 6 A microwave oven was used to warm a meal. If the
of protons, resulting in the atom being neutral. frequency of the radiation is 2.0 × 109 s–1, determine
the energy of one photon of this microwave radiation.
✓ The atomic number of the atom is the number of
protons (or electrons). 7 Explain why the spacing between a series of spectral
lines decreases as the wavelength becomes shorter.
✓ The mass number of the atom is the sum of the
protons and the neutrons. Answers to ITQs
✓ All atoms of a given element contain the same 1 12
C: 6 protons, 6 neutrons, 6 electrons
number of protons/electrons but can contain 13
C: 6 protons, 7 neutrons, 6 electrons
different numbers of neutrons. 14
C: 6 protons, 8 neutrons, 6 electrons
✓ The atomic mass of an element is the average 2 The atomic mass of an element is a weighted average
1
mass of one atom of the element relative to 12 th of the mass of its isotopes. This is unlikely to be a
the mass of one atom of the carbon-12 isotope whole number.
(12C).
3 As a moving particle in an electric field, the electron
✓ An element occurs as a mixture of isotopes. ‘should’ radiate energy and so move in an orbit of
Isotopes are atoms with the same number of ever-decreasing radius.
protons but different numbers of neutrons. Each
isotope has a different, characteristic relative
atomic mass (RAM).
Chapter 1 Atomic structure 11

Answers to Review questions


1 10.811 Da
3 (a) 1 × 105 J; (b) 2.19 × 105 J
4 ν = 5.09 x 1014 Hz
5 Atomic Mass Number of Number of Number of
Symbol Charge
number number protons neutrons electrons
15N 7 15 7 8 7 0
39 +
K 19 39 19 20 18 +1
3H+ 1 3 1 2 0 +1
23 +
Na 11 23 11 12 10 +1
90Sr2+ 38 90 38 52 36 +2

6 1.33 × 10–24 J
7 The difference in energy for the ninitial to the nfinal gets
progressively less with increasing distance from the
nucleus.
12

Chapter 2
The quantum atom and the periodic table
Learning objectives
■ State the Pauli exclusion principle and the Aufbau principle.
■ Write the electron configuration of a given atom or ion given its atomic number.
■ Illustrate electron configuration using an electron diagram.
■ Sketch the periodic table, illustrating the blocks and the elements in each group.
■ Discuss periodic trends in atomic and ionic radii.
■ Define ionization energy.
■ Define electron affinity.
■ Explain the general periodic trends in ionization energy and electron affinity among the main group
elements.
■ Define electronegativity and state the periodic trends in electronegativity.
■ Explain, using the elements of period 3 as an example, how ionization data can provide evidence for
sub-shells.
■ Predict the electronic configuration of an element from data on successive ionization energy.

The quantum atom


Bohr’s theory (discussed in Chapter 1), and the equations According to de Broglie, every particle is associated with a
he developed in 1913, were based purely on the idea of the wave. Its wavelength (λ) is given by the relationship:
electron as a particle. Bohr saw the electron as something h
λ= p
that had a definite position in space and moved in a
discernible fixed path. He offered no explanation of why where h is a constant (known as Planck’s constant,
an electron moving in an ‘orbit’ should thwart the laws of h = 6.63 × 10−34 m2 kg s−1) and p is the momentum of the
classical physics by remaining stable. particle (mass × velocity). His thesis was quickly supported
by the observation that electrons, so far regarded as
Matter and waves particles, could be diffracted. Diffraction is a fundamental
property of a wave.
In 1905 Albert Einstein, the famous German-born
theoretical physicist (1879–1955), had suggested a new idea This phenomenon is called wave–particle duality. The
about light. Although light is regarded as a wave motion particular properties, either wave or particle, which are
because it can be refracted and can suffer interference and displayed depend on the nature of the experiment being
diffraction, sometimes it shows the properties of a particle. used. The idea that anything can have two totally different
For example, some chemical reactions are light-initiated, sets of properties at one and the same time is outside our
but light below a certain frequency does not help the everyday experience. If I throw a black stone into a pond I
reaction, however intense that light may be. Einstein called do not expect it to re-appear as a scarlet ibis and fly away.
these ‘light-particles’ photons. But in everyday life, wave–particle duality is not of much
importance. The wavelength of a cricket ball coming from
In 1924 Louis de Broglie, a French physicist (1892–1987),
a fast-bowler’s hand is roughly 1 × 10−34 m, some 1028
extended this idea by suggesting the reverse: that material
times smaller even than an atom. So we do not expect the
particles can have wave properties. If de Broglie’s suggestion,
ball to be diffracted around the edge of the bat.
that all particles travel in waves, is correct then electrons
should also exhibit wave-like properties such as diffraction. In contrast, the wavelength of an electron is of the order of
tens of picometres (10−9 m), which is comparable with the
Chapter 2 The quantum atom and the periodic table 13

size of an atom. An electron is stable when its wavelength, The higher the frequency of the wave, the more energy
or a multiple of it, is an exact fit around a nucleus at a each photon carries. Because frequency is inversely
particular distance, but not otherwise. Figure 2.1 shows an proportional to wavelength this means that photons with
electron wave with three wavelengths around a nucleus at longer wavelengths carry less energy.
distance r3 and four wavelengths at distance r4. An electron This equation also tells us that the energy carried by a
with this wavelength could not fit in an orbit with a value stream of photons cannot have just any value. The energy
of r between these. comes in ‘packets’ of fixed size (hv) because each packet
comes from an identical electron transition between energy
levels. Such a packet is called a quantum of energy; the
r4
plural of quantum is quanta. Einstein’s idea that energy
is quantized rather than continuous has given us the
r3 quantum theory of matter.

The uncertainty principle


Not content with having to understand the idea of wave–
Figure 2.1 Electron waves fitting exactly around a nucleus at two
different distances. The wavelength is the same in both cases. particle duality, we also have to cope with a built-in lack
The same wavelength cannot fit in an orbit with a value of r of precision in measurements at the atomic level. In
between these two radii. 1927 Werner Heisenberg, a German theoretical physicist
(1901–1976), realized that because the devices we use to
Energy and wavelength measure particle properties (for example, photons) are
The wavelength of an electromagnetic wave and its very similar in size to the particles themselves, the very
frequency (i.e. the number of waves which pass a given interaction between the particle and the measuring device
point in one second) are related by the expression modifies the original properties of the particle. Heisenberg’s
uncertainty principle says that the more precisely
c=v×λ
the position of a particle is known (or experimentally
where c is the velocity of light, v is the frequency and λ is determined), the less precisely can its momentum be found
the wavelength (Figure 2.2). in the same experiment. The uncertainty principle is stated
mathematically as
h
Δp.Δx ≥ =

where the symbol Δ means ‘the uncertainty in’. Notice that h
(Planck’s constant) is involved yet again. Since momentum
(p) is a measure of particle energy, this equation tells us
that on the sub-atomic scale we cannot accurately know
both the position and the energy of a particle. In turn this
Figure 2.2 Frequency and wavelength. The diagram shows two
waves, one with half the wavelength of the other. If both are means that Bohr’s idea of a ‘particle’ travelling in a fixed
travelling at the same speed then in a given time, twice as many ‘orbit’ has to be modified.
of the short wavelength waves will pass a point in the direction of
travel than will the long wavelength waves. Orbits are dead, long live orbitals!
Einstein’s idea of the photon included the statement that the Erwin Schrödinger, an Austrian physicist (1887–1961),
energy carried by a single photon is given by the expression created a set of equations that help us to describe the
behaviour of electrons around atomic nuclei. Instead of
E=h×v
saying exactly where an electron exists at any moment in
where E is the photon energy, h is Planck’s constant and v time, the solutions of Schrödinger’s equations define the
is the frequency of the wave associated with the photon. probability of finding an electron. They can be used to

ITQ 1 A cricket ball has a mass of 160 g and a fast bowler can bowl ITQ 2 How is the rise of the quantum theory like the rise of
at 140 km/hour (38.9 m s−1). Use the de Broglie equation to confirm Dalton’s atomic theory?
the wavelength of the cricket ball. h = 6.63 × 10−34 m2 kg s−1.
14 Unit 1 Module 1 Fundamentals in chemistry

describe volumes of space in which there is a high probability


of finding the electron. The most useful graphical solutions
are called radial distribution plots.
The radial distribution plot shows the probability of finding Figure 2.4 A computer
an electron at a given radial distance r from the nucleus, generated simulation of the
plotted against distance from the nucleus. For the one probability of finding an electron
in its lowest energy state in a
electron of the hydrogen atom, the radial distribution plot hydrogen atom. The maximum
is shown in Figure 2.3. probability is at 53 pm from the
nucleus.

that an orbital can only contain one electron. To define


the energy of an electron exactly we need four numbers.
Radial distribution function

The first three define quite large differences in energy (the


numbers 1, 2, 3, … as used in Chapter 1), but the fourth is
different. It is called the spin of the electron. It has a value
of 12 and it makes only a minute difference to the energy.
So the orbital containing an electron with spin + 12 and the
orbital containing the electron with spin − 12 are so similar
to each other that the difference is lost in the fuzziness.
An orbital can contain two electrons, but they must have
opposite spins.
Radius, r
The orbital map
Figure 2.3 A plot showing the probability of finding the electron
of a hydrogen atom anywhere in a shell of radius r plotted Because we cannot know exactly what space an electron
against r, where r is the distance from the nucleus of the atom. occupies, the uncertainty principle tells us that we can
The hydrogen atom is spherically symmetrical; this means know its energy with great precision. Although the actual
that there exists a sphere around the nucleus in which energies of electrons around a nucleus vary with the
there is a high probability of finding the electron. Because nucleus, the pattern of their magnitudes is always the same.
of the uncertainty principle, this sphere is not sharp-edged, We will compare the pattern with the one we developed in
but ‘fuzzy’. This ‘fuzziness’ is shown in Figure 2.4. For the Chapter 1. The energies can be shown on a ‘ladder’ with
hydrogen atom, the maximum probability of finding the energy levels as rungs. The rungs are numbered 1 to 8,
electron is at a distance of 53 pm from the nucleus, which but we will only need to look at the first five. These are
coincides with the Bohr radius for this atom. shown in outline in Figure 2.5. This number is called the
principal quantum number and is given the symbol n.
The volume of space that contains a good probability
of finding an electron is called an orbital. We shall be
concerned with the numbers and shapes of the orbitals n=5
n=4
as well as the electrons they contain. Usually we think of
an orbital as the volume of space which contains a 95% n=3

probability of containing the electron. Notice that nowhere


in this discussion do we try to describe the electron itself, n=2
only its position.

Pauli’s exclusion principle


Wolfgang Pauli, an Austrian theoretical physicist (1900–
1958), pointed out that in any one atom, no two electrons n=1
can have exactly the same energy. This statement is known
as the Pauli exclusion principle.
Figure 2.5 An energy ladder showing the first five main divisions
An orbital like the one in Figure 2.4 is defined using the of energy levels. The lowest energy level is shown at the bottom.
energy of the electron as one factor, but that does not mean The levels get closer as they get nearer to the top.
Chapter 2 The quantum atom and the periodic table 15

Any electron that occupies any one of these levels is found


in a spherical orbital like that in Figure 2.4. These orbitals are
3d
called s orbitals. (Memory hint: think of ‘s’ for spherical.)
3p
For level 1 there are no other energy levels. 3s

For level 2 and all subsequent levels, there is another


energy level a little way above the s level. It is not spherical.
2p
It has three components, all at right angles to each other.
2s
We say that they are along the x-, y- and z-axes. Each of the
three components is at exactly the same energy level. Each
associated orbital looks a bit like an egg-timer (Figure 2.6).
We usually draw these orbitals as shown in Figure 2.6, but
notice that the two lobes together make up one orbital.
1s
Like any other orbital it can accommodate two electrons,
so the energy level as a whole can hold six electrons. In
the old terminology of ‘shells’ (page 8, Chapter 1), these
would be ‘sub-shells’. These orbitals are called p orbitals. Figure 2.8 The first three levels of the energy ladder with d levels
added. The levels are identified as 1s, 2s, 2p, 3s, 3p and 3d.
(Memory hint: they are shaped like propellers.)
The fourth main level has another set of levels above its d
Figure 2.7 shows these p orbitals added to the first three
levels. The associated orbitals are called f orbitals. (Memory
levels of the energy ladder.
hint: they have funny shapes.) We shall not need to
These energy levels are sufficient to define the electron consider these orbitals any further.
configurations for the first 18 elements (from hydrogen to
When we draw the energy ladder we take account of the
argon) in the periodic table.
fact that the 4s level is lower than the 3d level (Figure 2.9).
Above the level of the third group, another set of levels This has some interesting consequences, which we will see
appears. In it there are five levels which are separate but in Chapter 17 about the transition elements.
identical in energy. Look at the pattern of numbers of levels:
level 1 has 1, level 2 has 1,3 and level 3 has 1,3,5, …). The
6p
associated orbitals are called d orbitals. (Memory hint: one 5d
of them is shaped like a donut.) Figure 2.8 shows the energy 4f
6s
ladder with the 3d levels added. 5p
4d
5s

4p
4s 3d

3p 3p
Energy

3s 3s
z
2p
2s
2p

2s

y
1s
x Figure 2.9 Relative energy levels for n = 1 to 6.

1s The aufbauprinzip principle


Bohr and Pauli formulated the aufbauprinzip (which means
‘building up’ principle). This principle governs the order in
Figure 2.6 Shape of Figure 2.7 The first three which energy levels are filled when building up electrons
p orbitals, both in outline levels of the energy ladder around an atom. Each orbital can hold two electrons, with
and in probability. with p levels added. The
levels are identified as 1s, 2s,
opposite spin. One spin gives slightly less energy than the
2p, 3s and 3p. other so, at any level, electrons half-fill each orbital first.
16 Unit 1 Module 1 Fundamentals in chemistry

To build up the electron structure for an atom, fill a diagram structure of the preceding noble gas. The sodium structure
like that in Figure 2.9 one electron at a time. Start at the would then be written as Ne 3s1.
bottom of the ‘ladder’ (1s) and the left-hand side of each The electronic structure of atoms is linked to their position
rung. Move on to the next rung horizontally and then in the periodic table. This topic is looked at next in this
the next vertically until all the electrons are added. Using chapter.
sodium (Z = 11) as an example, the order of filling is
1s1 → 1s2 → 2s1 → 2s2 → 2px1 → 2py1 → 2pz1 → 2px2 → Developing the periodic table
2py2 → 2pz2 → 3s1
During the middle of the nineteenth century more
Figure 2.10 shows the diagram for a sodium atom. elements were being discovered. With this discovery came
the challenge of memorizing their names and properties.
6p Attempts were made to develop a systematic manner of
5d
4f grouping and classifying the elements according to their
6s
5p
properties. What we now are familiar with as the periodic
4d table developed over many years.
5s

4p One of the earliest attempts at ordering elements was


4s 3d
made by Johann Wolfgang Dobereiner, a German chemist
3p
(1780–1849). In 1829 he published work that grouped
Energy

3s
elements with similar properties in blocks of threes (triads),
2p as shown in Figure 2.13. He had noticed that the average
2s atomic mass of lithium and potassium was similar to the
atomic mass of sodium, and that these three elements had
similar properties. He found that this observation was true
1s for other groups of three elements.
Figure 2.10 The electron ladder for a sodium atom. Li Ca S Cl Mn

Writing electron structures Na Sr Se Br Cr


The series of electrons shown above can very neatly be
abbreviated as 1s2 2s2 2p6 3s1. This shows the energy level, K Ba Te I Fe
the orbital type and the number of electrons in those Figure 2.13 Dobereiner’s triads – a very early version of the
orbitals, using the symbols shown in Figure 2.11. periodic table.

number of Quite a few years later (in 1865), John Newlands, an English
electrons
chemist (1837–1898), gave a lecture outlining his idea that
energy level 2p6
type of when the elements were listed in order of increasing atomic
orbital mass, some similar elements were separated by intervals of
Figure 2.11 Symbols showing the occupancy of an atomic orbital. eight (Law of octaves). His work wasn’t accepted because
Figure 2.12 illustrates a readable way of showing an of some odd groupings. For example, he put oxygen, sulfur
electron structure. This approach, which has the advantage and iron in the same group.
of also showing electron spin, is to draw the orbitals as a The most successful arrangement of the elements, however,
horizontal series of boxes, and fill them one at a time. Work was the one developed in 1869 by two outstanding scientists
from left to right and always put in the first arrow pointing and teachers Dmitri Ivanovich Mendeleev (Russian,
downwards to indicate the low-spin state. You will also see 1834–1907) and Lothar Meyer (German, 1830–1895).
this notation used on page 161. Working independently (and without knowing about
1s 2s 2p 3s Newlands’ work), they both discovered that when the
known elements were arranged in order of increasing
atomic weights, certain similarities in properties were
Figure 2.12 Electrons in boxes for Na, Z = 11.
repeated in cycles of eight. Mendeleev published his version
When larger atoms are involved, not much of this needs of the periodic table before Meyer and so he is credited for
to be spelt out. You only need to show detail above the its discovery.
Chapter 2 The quantum atom and the periodic table 17

I VIII
1 Atomic number 2
Hydrogen Element name Alkali metals Other metals Helium
H II Symbol Alkali-earth metals Semimetals III IV V VI VII
He
1.0 4.0
Atomic weight
3 4 5 6 7 8 9 10
Lithium Beryllium
(mean relative mass) Transition metals Non-metals Boron Carbon Nitrogen Oxygen Fluorine Neon
Li Be Rare earths Noble gases B C N O F Ne
6.9 9.0 10.8 12.0 14.0 16.0 19.0 20.2
11 12 Radioactive rare earths Hydrogen 13 14 15 16 17 18
Sodium Magnesium Aluminium Silicon Phosphorous Sulfur Chlorine Argon
Na Mg Al Si P S Cl Ar
23.0 24.3 27.0 28.1 31.0 32.1 35.4 39.9
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.1 40.1 45.0 47.9 50.9 52.0 54.9 55.9 58.9 58.7 63.5 65.4 69.7 72.6 74.9 79.0 79.9 83.8
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 36
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.5 87.6 88.9 91.3 93.0 95.9 [97.9] 101.1 102.9 106.4 107.9 112.4 114.8 119.0 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Caesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At Rn
132.9 137.3 138.9 178.5 181.0 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 [209.0] [210.0] [222.00]
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmsladtium Roentgenium Copernicium Ununtrium Flerovium Ununpentium Livermorium Ununseptium Ununoctium
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
[223.0] [226.0] [227.0] [265.1] [268.1] [271.1] [270.0] [277.2] [276.2] [281.2] [280.2] [285.2] [284.2] [289.2] [288.2] [293.0] [294.0] [294.0]

58 59 60 61 62 63 64 65 66 67 68 69 70 71

LANTHANIDES
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140.91 144.24 [144.91] 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Brekelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
ACTINIDES
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.04 231.04 238.03 [237.05] [244.06] [243.06] [247.07] [247.07] [251.08] [252.08] [257.10] [258.10] [259.10] [262.11]

Figure 2.14 A modern version of periodic table.

Unlike Newlands, Mendeleev’s work was accepted because As nuclear reactions were studied, tiny amounts of a
he deliberately left spaces in his table and then made manganese-like element fitting into the space were found,
predictions about the existence and properties of elements and it was named technetium. It is radioactive, and the
that would be discovered to fill the spaces. Several years half-life of its most stable isotope is 4.2 million years. Since
later, elements were discovered with properties that bore the age of the Earth is estimated as 4.5 × 109 years, its
remarkable similarity to his predictions. present-day absence is unsurprising.
In a modern periodic table, the elements are arranged Since then at least 30 other elements have been discovered
in order of increasing atomic number instead of atomic that are results of the radioactive decay of ‘natural’ elements,
weight. However, at the time of Mendeleev’s work, atomic or created through nuclear reactions. All these elements are
numbers were not known because protons and electrons themselves radioactive. Some are familiar, such as element
had not yet been discovered. The concept of isotopes was 86, radon (which was until 2002 the heaviest of the noble
also unknown, so many of the atomic weights used were gases). However, most are transient, with half-lives often
incorrect. measured in seconds. Some are unbelievably rare: only 4
atoms of element 118 (Uuo) have ever been produced. Its
The modern periodic table neighbour in the periodic table, Uus (ununseptium, Latin
for 117) has only very recently been announced (2013).
A modern form of the periodic table is shown in Figure 2.14. It is the last member of the halogen series and it would
presumably be a metal, if enough atoms could ever be made.
Synthetic elements
Until 1936, nearly 30 years after Mendeleev’s death, one of Structure of the periodic table
the gaps he had left remained unfilled. Element 43, which Elements in the periodic table are arranged in order of
would be placed between molybdenum and ruthenium increasing atomic number. Horizontal rows of elements are
and directly below manganese, was still undiscovered. The called periods and vertical columns of elements are called
element, which Mendeleev called ‘ekamanganese’, could groups. The elements in a group have similar electronic
not be found on Earth. configurations and similar properties.
18 Unit 1 Module 1 Fundamentals in chemistry

Groups Periodicity
Older systems assigned a Roman numeral (I–VIII) to each
When chemical and physical properties of atoms are
group and added the suffix A for the main groups and B for
plotted against atomic numbers, repeat patterns (known as
the transition elements (in the centre of the periodic table).
periodicity) are often observed. These patterns are due to
In 1985, the International Union of Pure and Applied
the fact that the electronic configurations of the atoms are
Chemistry (IUPAC) adopted a simpler system in which the
being repeated. Elements in a group have similar chemical
columns are labelled from 1 to 18 from left to right. This
properties since all members of the group have similar
system is used by the majority of the international scientific
valence shell electronic configurations. For example, all the
community. Also in use is a numbering system where the
elements in Group I have one electron in the outer shell.
Roman numerals are converted to Arabic numbers, so that
Group VII is referred to as Group 7. The periodic table in It is the outermost electrons (electrons in highest energy
the CAPE Chemistry Syllabus uses the I–VII system; we levels) of the atom that have the greatest influence on its
will use this system in this book, but on occasions give the properties since these electrons are the easiest to remove
IUPAC group number in brackets. or become attracted by nuclei of other atoms or molecules.
Also it is easier to add electrons to the outermost energy
Blocks
levels.
For convenience, the elements are referred to as being in
Changes to properties resulting from addition of electrons to
blocks.
inner orbitals, for example d orbitals, are usually much less
■ Elements in Groups I and II (1 and 2) are in the marked than those associated with the addition of electrons
s-block since these elements have configurations ns1 to outer s and p orbitals. Across a period there are significant
and ns2 respectively. differences in the chemical properties of the elements.
■ The p-block refers to the elements in Groups III–VIII
(13–18). These have electronic configurations ranging The law of chemical periodicity
from ns2 np1 for Group III to ns2 np6 for Group VIII. The properties of elements are a periodic function of their
■ The d-block consists of elements in Groups IIIB–IIB atomic numbers.
(3–12) with the configuration (n−1)d1 ns2 to
Periodic patterns are observed for several physical
(n−1)d10 ns2. There are some irregularities in this
properties of the individual atoms of the elements. Here
block.
are some examples:
■ The f-block elements generally (though there are
some irregularities) have electronic configurations ■ the sizes of the atoms and ions (atomic and ionic radii);
(n−2)f1 (n−1)d10 ns2 to (n−2)f14 (n−1)d10 ns2. ■ the strength with which the outermost electrons are

Elements in the s- and p-blocks are referred to as main held by the isolated atom (ionization energy);
group (or representative) elements. Among the main ■ the ease with which electrons can be added to these

group elements are the alkali metals (Group I or Group isolated atoms (electron affinity).
1), the alkaline earth metals (Group II or Group 2), the The magnitude of these properties are related to the net
halogens (Group VII or Group 17) and the noble gases attractions between the outer shell electrons.
(Group VIII or Group 18). Elements in the d-block are
the transition elements and the f-blocks contain the Periodic properties in atomic ‘size’
lanthanides and actinides.
Atomic radius
Periods
An atom does not exist in isolation neither does it have a
Each period starts with an element with the ns1 sharply defined boundary (see page 17 above). The size of
configuration and ends with one with the ns2 or ns2  np6 an atom can be estimated by assuming that it is spherical
noble gas configuration. and that, when identical atoms are bonded together, the
The period number refers to the principal quantum level n, radius of one atom can be approximated to be half the
which contains the outermost electrons. distance between neighbouring atoms. These radii can be
determined from X-ray scattering measurements. Since
atoms bond with each other in a variety of ways (see
Chapter 4), different types of atomic radii can be defined.
Chapter 2 The quantum atom and the periodic table 19

K
200
Ar

Ne Na Ca

Atomic radius / pm
150
He Mg
Li
Si
Al S
100 Be P
Cl
C O
B
2r 2r N F
50
Figure 2.15 Covalent radius. Figure 2.16 Metallic radius. H

■ Covalent radius is half the distance between nuclei of 0


0 2 4 6 8 10 12 14 16 18 20
adjacent identical atoms bonded together in a covalent
Element
molecule (Figure 2.15).
Figure 2.18 Trends in atomic radius, showing the changes
■ Metallic radius is half the distance between the across periods 2 and 3. Note that the noble gases don’t form
nuclei of adjacent metal atoms in a crystal of a metal compounds, so the values shown are van der Waals radii.
(Figure 2.16). atomic size decreases
■ Ionic radius is the radius of ions in crystalline ionic
compounds, related to the distance between the nuclei I II III IV V VI VII VIII

of neighbouring cations and anions in the crystal H He


(Figure 2.17). Li Be B C Ne
N O F
atomic size increases
I– I– Mg
Na Al Si P Ar
S Cl

+ K Ca Ga Ge As Se
Li + Br Kr
K

Rb Sr In Sn Sb Te I Xe

iodide ion +
diameter sum of K Cs Ba Tl Pb Bi Po At Rn
and I– radii

Figure 2.17 Ionic radii are measured indirectly be comparing


internuclear distances in salts whose positive ions vary in size. Figure 2.19 Periodic trends in atomic radius for the main group
Here we can measure the diameter of the iodide ion directly and elements. The trends both down groups and across periods can
so calculate the ionic radius of the potassium ion. be seen. Note that the noble gases don’t form compounds, so
the values shown are van der Waals radii.
■ van der Waals radius is the radius of adjacent atoms
which are not chemically bonded in a solid but are in An element such as the metal sodium will have a metallic
‘contact’ with each other. In the noble gases (Group radius, an ionic radius when it is bonded in sodium chloride
VIII), for example, atoms are not chemically bonded to and a covalent radius when present in its vapour phase.
each other and their van der Waals radii are estimated The discussions of periodic trends in atomic radius of the
as half the distance between the nuclei of adjacent elements that follow refer to the covalent radii of the
atoms of solidified samples of the gases. These radii elements.
are much larger than covalent radii and are sometimes
There are some distinct trends in the variation of atomic
not included in discussions of periodic trends of the
radius (Figures 2.18 and 2.19):
elements.
■ atomic radius generally increases down a group;
The above definitions of atomic and ionic radii are only
■ atomic radius generally decreases across a period from
approximations. Atoms approach each other more closely
in the bonded than the non-bonded state. The atomic left to right.
radius of an element may vary depending on the compound We can explain these trends by consider two opposing factors
in which it is present. For example, the atomic radius of that contribute to the size of atoms. These are the number
carbon in diamond is 77 pm, in ethane (C–C) it is also of occupied electron shells, i.e. the principal quantum
77 pm, in ethene (C=C) it is 69 pm and in ethyne (C≡C) it number (n) of the orbitals in which the outermost electrons
is 60 pm. are present, and the effective nuclear charge.
20 Unit 1 Module 1 Fundamentals in chemistry

A higher principal quantum number (n) correspond to When an electron is added to the neutral atom the total
larger orbitals that lie further from the nucleus. With number of electrons increases but the number of protons
increasing value of n, electrons are therefore at greater remains the same. The result is an excess of negative charge
distances from the nucleus. and a negatively charged species or an anion is formed.
The nuclear charge is equal to the number of the protons ■ A positive ion (cation) is smaller than the neutral atom
in the nucleus of the atom. The effective nuclear charge from which it was derived.
is the residual net charge felt by the outer valence electrons. ■ A negative ion (anion) is larger than the neutral atom
For atoms containing more than one electron, the effective from which it was derived.
nuclear charge (Zef) is less than the full nuclear charge (Znc).
Removal of an electron from the neutral atom results in a
Electrons in inner shells ‘shield’ the outer electrons from
reduction in the number of electrons and hence a reduction
the nucleus as a result of electron–electron repulsions.
of electron–electron repulsions. Since the number of
The higher the effective nuclear charge the greater is protons in the positively charged nucleus of the atom has
the attractive force between the outer electrons and the not been changed, the electron–nuclear attractions in the
positively charged nucleus, hence the smaller the atomic cation will be strengthened. The cation has a smaller size
radius will be (for a fixed value of n). than the neutral parent atom. For example, the Na+ ion
Down a group, electrons are present in orbitals with (95 pm) is smaller than the neutral Na atom (186 pm). For
progressively higher principal quantum numbers, which the same value of n, the greater the positive charge on the
are progressively further from the nucleus. Though the cation, the smaller is its radius. For example, the Na+ ion
nuclear charge is increasing down the group, the outer (95 pm) is larger than the Mg2+ ion (65 pm), which in turn
electrons will not experience the full attractive force of the is larger than the Al3+ ion (50 pm).
nucleus as a result of shielding from electrons in shells of Table 2.1 Atomic radii of Li and Na compared with cation radii
lower n. The main contributing factor to the increase in Electronic Nuclear Number of Atomic
Atom/ion
atomic radius down the group, therefore, is the increased configuration charge electrons radius / pm
value of the principal quantum number. Among the Group Li 1s2 2s1 +3 3 152
I elements, for example, Li has its outermost electron in the Li+ 1s2 +3 2 60
2s orbital whereas for Na this electron is in the 3s orbital Na 1s2 2s2 2p6 3s1 +11 11 186
(n = 3). Similarly, for K, its outermost electron is in the Na+ 1s2 2s2 2p6 +11 10 95
4s orbital. The order of increasing atomic radius for these For a negative ion, addition of one or more electrons to the
atoms is K > Na > Li. neutral atom increases the electron–electron repulsions.
Atomic radius decreases from left to right across a period. The electrons are more spread out and the anion is larger
Across a period, from left to right, there is no change than the corresponding neutral atom. The greater the
in the principal quantum number, n, of the outermost negative charge on the anion, the larger is its radius. For
orbitals. However, the nuclear charge of each element example, the N3− ion (171 pm) is larger than the O2− ion
increases across a period. Electrons are being added to s (140 pm), which in turn is larger than the F− ion (136 pm).
or p orbitals in same principal quantum level, and these
Table 2.2 Atomic and anionic radii for nitrogen, oxygen and
orbitals are at approximately the same distance from the flourine
nucleus. Shielding from other electrons in the same shell Electronic Nuclear Number of Atomic/ionic
is insignificant. The effective nuclear charge therefore Atom/ion
configuration charge electrons radius / pm
increases across the period, resulting in electrons being N 1s2 2s2 2p3 +7 7 70
pulled closer to the nucleus. N3− 1s2 2s2 2p6 +7 10 171
O 1s2 2s2 2p4 +8 8 66
Ionic radii O2− 1s2 2s2 2p6 +8 10 140

A neutral atom contains an equal number of protons and F 1s2 2s2 2p5 +9 9 64

electrons. When an electron is removed from a neutral F− 1s2 2s2 2p6 +9 10 136

atom, the number of remaining electrons decreases but Atoms and ions with the same number of electrons are
the number of protons (nuclear charge) remains the same. isoelectronic. O2−, F−, Ne, Na+ and Mg2+ all have 10
This excess of protons results in the atom being positively electrons arising from their configuration 1s2 2s2 2p6. Since
charged and this positively charged ion is called a cation. these ions have the same number of electrons, they all have
Chapter 2 The quantum atom and the periodic table 21

Li
+
Be
2+
N
3–
O
2–
F
– ■ The Group VIII elements have the highest ionization
energies in their period.
60 152 31 111 171 70 140 66 136 64
Na
+
Mg
2+
Al
3+
S
2–
Cl
– ■ There is a general increase in ionization energy from
left to right across a period from Group I to Group VIII.
95 186 65 160 50 143 184 104 181 99
+ 2+ 3+ 2– –
The value then falls again after Group VIII to the start of
K Ca Ga Se Br
the next period. The pattern resembles that of sawtooth
133 231 99 197 62 122 198 117 185 114 (Figure 2.21), similar to that observed for atomic radii.
+ 2+ 3+ 2– –
Rb Sr In Te I ■ There is a gradual decrease in ionization energy down
a group.
148 244 113 215 81 162 221 137 216 133
There are some exceptions to these trends. Group III
Figure 2.20 Ionic radii. The ions are coloured red (cations) and elements have lower first ionization energies than the
blue (anions). The parent atoms are coloured brown. The radii are
given in picometres. preceding Group II elements. For example, the ionization
energy of boron, B, is lower than that of beryllium, Be,
the same amount of electron–electron repulsions. However, despite it having a greater effective nuclear charge. The
they have different nuclear charges and sizes. Mg2+, with ionization energy of the Group VI elements are lower than
the greatest nuclear charge in the series, will experience those of Group V. For example, oxygen, even though it
the greatest electron–nuclear attraction and is therefore has a greater effective nuclear charge than nitrogen, has a
the smallest. O2−, with the smallest nuclear charge, will lower first ionization energy.
experience the lowest electron–nuclear attraction and is
He
therefore the largest. 2400
Ne
For an isoelectronic group of ions, the greater the nuclear
Ionization energy / kJ mol –1

2000
F
charge on the ion, the smaller is the ion.
Ar
1600 N
Cl
Ionization energy 1200 H C O
P
Be
The formation of bonds between atoms depends on the size Mg Si S
800 Ca
of the energy changes as an individual atom gains, loses or B
Al
shares electrons. 400 Li Na K

Ionization energy (IE) is the minimum energy required to 0


remove an electron from an atom in its gaseous phase. 0 2 4 6 8 10 12 14 16 18 20
Nuclear charge, Z
A(g) → A+(g) + e− Figure 2.21 Ionization energies of the first 20 elements.
IE = E(A+) − E(A), where E stands for energy Generally, across a period there is an increase in the effective
Removing an electron from the outermost orbital of an nuclear charge while n remains constant and the atom gets
atom requires an input of energy in order to overcome smaller. Removal of an electron from the smaller atom will
the electron–nucleus attraction. The first ionization energy become progressively harder so ionization energy increases
(IE1) is the energy required to removed the least tightly across the period.
bound (outermost) electron from the neutral atom. The Down a group, outermost electrons are present in orbitals
second ionization energy (IE2) is the energy required to that are progressively further from the nucleus. These
ionize the cation resulting from IE1. An atom will have as outer electrons are also shielded from the nucleus by inner
many ionization energies as it has electrons. electrons. As a result, they are more easily removed so
The general trends in ionization energy among the main ionization energy decreases down a group.
group elements are summarized as follows: In general, small atoms have large ionization energies and
■ The elements of Group I have the lowest ionization large atoms have small ionization energies.
energies in their period.

ITQ 3 Arrange the following elements ITQ 4 Consider the following ions: Na+, Cl−, O2−. ITQ 5 Suggest a reason why the gas
in order of increasing atomic radius: (a) Which ion will be the smallest? phase is used for measurements of
Na, Cl, K, Br (b) Which ion will be the largest? ionization energy.
22 Unit 1 Module 1 Fundamentals in chemistry

furthest from the nucleus. The cation Na+ resulting from this
Worked example 2.1
process has electrons in the n = 2 shell, which is closer to the
Which of the following atoms would have the lowest first
Q ionization energy?
nucleus and has the electronic configuration of the noble
gas neon. It is not surprising therefore that the removal
A [He] 2s2 2p4 of the second electron (IE2) from this stable inner core
B [Ne] 3s2 3p5 requires a significantly higher energy than the first. Similar
C [Xe] 6s2 patterns will be observed for all elements of Group I since
D [Ne] 3s1 they all have the general [X] ns1 electron configuration and
the same single outer valence electron.
The correct answer is C, since its outermost electron is in the
A n = 6 shell. This shell is furthest from the nucleus, and so Aluminium is a Group III (13) element, with three valence
experiences greater shielding from inner shells and a lower electrons. A big change in ionization energy occurs after
effective nuclear charge. It would require less energy to remove the third ionization process since this requires removal
an electron from this, the largest atom of those in the example.
of an electron from the Al3+ cation which has a noble gas
electronic configuration.
Variation in successive ionization energies
A(g) → A+(g) + e− IE1 Electron affinity
A+(g) → A2+(g) + e− IE2 Ionization energies (IE) are the energy changes involved
in the formation of positive ions. Ionization energies are
A2+(g) → A3+(g) + e− IE3
always positive, meaning that energy is taken into the
Successive ionization energies of an element increase in system:
the order IE1 < IE2 < IE3 < IE4. Removal of the first electron
M → M+ + e− + ΔH
from the neutral atom gives a smaller positively charged
ion. Removal of an electron from this smaller positively ΔH is always positive.
charged ion will require more energy so IE2 > IE1. Successive However, many elements, especially those towards the
ionization energies will increase since the electron is being right-hand side of the periodic table, are able to form
removed from a more positive ion. anions. When one mole of a monatomic species gains one
The greatest difference between successive ionization electron to form an anion, the energy change is called the
energies for a given atom occurs after the removal of all first electron affinity (EA) of the element.
the outer valence electrons. Here is the data for the first The first electron affinity is an exothermic process, meaning
four ionization energies of sodium. that in the reaction
Na(g) (1s2 2s2 2p6 3s1) → Na+(g) (1s2 2s2 2p6) + e− X + e– → X– + ΔE
IE1 = 495.8 kJ mol−1
the value of ΔE is negative.
Na+(g) (1s2 2s2 2p6) → Na2+(g) (1s2 2s2 2p5)+ e−
For example, the first electron affinity (EA1) of chlorine is
IE2 = 4562 kJ mol−1
–349 kJ mol–1.
Na2+(g) (1s2 2s2 2p5) → Na3+(g) (1s2 2s2 2p4) + e−
The first electron affinity refers to the energy released on
IE3 = 6910 kJ mol−1
the addition of one electron to a neutral atom, the second
Na3+(g) (1s2 2s2 2p4) → Na4+(g) (1s2 2s2 2p3) + e− electron affinity refers to the energy change when a second
IE4 = 9543 kJ mol−1 electron is added to the negatively charged ion, and so on.
As is expected, the values of the successive ionization These subsequent values of electron affinity (EA2, EA3,
energies increase as the species produced from the ionization …) are always positive, meaning that heat is taken in as
process becomes progressively more positively charged and an anion becomes multiply charged. The change from
smaller. Removal of the first electron from the 3s orbital of negative to positive is because for later EA changes, the
the sodium atom is the easiest process, since this orbital is electrons are being forced in against the repulsion of a
negatively charged ion.
ITQ 6 Suggest an explanation for the decrease in first ionization
energy between P and S. You need to think about which electron
is being removed. Why might it be easier to remove the electron
from S?
Chapter 2 The quantum atom and the periodic table 23

Periodic trends in electron affinity Worked example 2.2


Variations in electron affinity follow a similar trend as
Suggest a reason for the large decrease in electron affinity
ionization energy and parallels variation in atomic radius. In Q between lithium and beryllium.
general the smaller atoms (except for the period 2 elements)
Li has the electronic configuration 1s2 2s1 and Be has the
with the greater effective nuclear charges will attract an A electronic configuration 1s2 2s2. Li has a smaller nuclear
added electron and so will have greater electron affinities
charge than Be. One would expect the Be atom with the
than the larger atoms with smaller effective nuclear charge
greater nuclear charge to attract an additional electron more
and greater electron–electron repulsions. In general: readily than Li. This is not what is observed, however, and
■ electron affinity increases across a period (Figure 2.22); Be has a lower electron affinity than Li. If we consider the
electronic configuration of each atom, we will see that the
400
additional electron to be added to Li will enter the half-filled 2s
orbital and fill it. For Be the additional electron will enter a 2p
Electron affinity / kJ mol –1

F
300 orbital which is of higher energy and further from the nucleus
than the 2s orbital. The 2p orbital will also experience greater
electron–electron repulsions from the two electrons already
200
C present in the 2s orbital. The result of this is the lower electron
O affinity of Be.
100
H Li
Be(g) (1s2 2s2) + e− → Be−(g) (1s2 2s2 2p1)
He Be
B
N Li(g) (1s2 2s1) + e− → Li−(g) (1s2 2s2)
Ne
0
0 1 2 3 4 5 6 7 8 9 10
Atomic number
Electronegativity
Figure 2.22 Electron affinities for period 2.
Electronegativity is the tendency of an atom to pull the
400
electrons in a bond towards itself.
Cl
F Br
Linus Pauling, an American chemist and biochemist
Electron affinity / kJ mol –1

I
300
At (1901–1994), developed a scale of electronegativity in
which elements are assigned different values (Figure 2.24).
S Se Fluorine has the highest value and Group I (Group 1)
200
Te Po elements have the lowest. In general, the electronegativity
O
of an element increases across a period from left to
100
right and decreases down a group. Elements with high
electronegativities will readily attract electrons in a bond.
0 This concept will be further discussed in Chapter 4 when
1 2 3 4 5 6 7
Period (row) on periodic table
we look at chemical bonding.

Figure 2.23 Electron affinities for Groups VI and VII.


I
increasing electronegativity
■ electron affinity decreases down a group (Figure 2.23);
H
■ elements with the electronic configuration ns2 2.1
II III IV V VI VII
(Group II/2), (Group V/15) or np3
(Group VIII/18) np6
Li Be B C N O F
increasing electronegativity

have the lowest electron affinities, e.g. Be, N, Ne; 1.0 1.5 2.0 2.5 3.0 3.5 4.0

■ elements with the electronic configuration np4


Na Mg Al Si P S Cl
(Group VI/16) and np5 (Group VII/17) have the 0.9 1.2 1.5 1.8 2.1 2.5 3.0

highest electron affinities, e.g. O, F.


K Ca Br
0.8 1.0 2.8
ITQ 7 The electronic configurations for three neutral atoms are
given below. I
2.5
I 1s2 2s2 2p6 3s2
II 1s2 2s2 2p6 3s2 3p3 Figure 2.24 The Pauling scale of electronegativity.
2 2 6 2 6
III 1s  2s  2p  3s  3p
Which of these atoms would have the largest 3rd ionization ITQ 8 The electron affinity of nitrogen is less than that of carbon.
energy? Suggest a reason for this observation.
24 Unit 1 Module 1 Fundamentals in chemistry

Summary of general periodic trends of the electron configuration of the element combined
with the competing electron–nuclear attraction and
Among the main group elements of the periodic table: electron–electron repulsion. The stronger the electron–
■ atomic radius decreases across a period and increases nucleus attraction the smaller the atom is and the
down a group (with some exceptions); greater the ionization energy and the electron affinity.
■ the first ionization energy increases across a period and On the other hand, if the electron–electron repulsions
decreases down a group (with some exceptions); are greater than the electron–nucleus attraction,
■ successive ionization energies show the greatest increase the larger the atom is and the smaller the ionization
when the inner core electrons are being removed; energy and the electron affinity.
■ elements of Group I (Group 1) and Group II (Group 2) ■ As a result, we can predict the properties of elements
have the lowest ionization energies and the smallest based on their position in the periodic table and so we
electron affinities. They will therefore lose electron(s) do not have to memorize information on each and
readily to form +1 and +2 ions; every element (see Table 2.3).
■ elements of Group VI (Group 16) and Group VII
Table 2.3 Periodic trends in summary
(Group 17) have high ionization energies and large
Property Across period Down group
electron affinities and so they will easily gain electrons
Zeff increases increases slightly
to form negatively charged species;
n (principal quantum number) remains constant increases
■ the noble gases (Group VIII / Group 18) have very
atomic radius decreases increases
high ionization energies and very low electron
ionization energy increases decreases
affinities (endothermic process) indicating that they
electron affinity increases decreases
neither lose nor gain electrons.
electronegativity increases decreases
■ Periodic properties such as atomic radius, ionization
energy and electron affinity can be explained in terms

Quantum effects in chemical bonds


In the next chapter we shall study several types of chemical bond, all based on the idea of electrostatic attraction
between positively charged and negatively charged regions of atoms. For example, protons in atomic nuclei ‘attract’
electrons shared with other atoms. However, modern calculations show that other factors must sometimes be at
work. Here is one example.
Intriguingly, the covalent component of the interatomic force between two fluorine atoms in the fluorine molecule
is repulsive, not cohesive. Some other effect must be at work between the two atoms, overcoming this repulsion
and making an overall attraction.
When two or more versions of the same molecule exist, which differ only in the possible arrangement of their
electrons, the molecule is more stable than predicted. We say that the different electronic versions of the molecule
resonate with each other. The molecule exists, at any one moment in time, as a fusion of the various possible
extremes. You will see this in action when you read about the structure of benzene (page 235).
Quantum calculations show that in ‘covalent’ bonds such as F–F and hydrazine (H2N–NH2) the electron density
in the bond region is very little different from the rest of the molecule. In these molecules the bond is reinforced
by a strong resonance between covalent ‘electron share’ and ionic ‘electron transfer’ forms. The bond is not a
consequence of the low energy of the molecule but is a consequence of the resonance energy.
This resonance stabilization is found increasingly as the bonded atoms move from left to right and from bottom to
top in the periodic table. The effect has been named the charge-shift bond.

ITQ 9 Account for the fact that the first electron affinity, EA1, can
be either positive or zero whereas the second electron affinity,
EA2, is always negative (requires an input of energy).
Chapter 2 The quantum atom and the periodic table 25

Summary
✓ Electromagnetic radiation has the properties of ✓ Three features of the atomic orbital are described
both waves and particles. by quantum numbers: size (n), shape (l)
orientation (ml).
✓ Light exists as photons (quanta) which have
energy proportional to their frequency. ✓ Orbitals are part of sub-shells defined by n and l,
which are part of an energy level defined by n.
✓ According to quantum theory, an atom can have
only certain amounts of energy (E = nhν) which ✓ An orbital can accommodate a maximum of two
can only be changed if the atom absorbs or emits electrons. More generally, this can be expressed
light. as no two electrons can have the same four
quantum numbers simultaneously. That is, in an
✓ Allowed energy levels are related to allowed
orbital containing two electrons, the electrons
wavelengths of the electron’s motion.
must have opposite spins.
✓ Electrons exhibit diffraction patterns (as do
waves of energy), and photons exhibit transfer of
✓ The quantum mechanical atom provides the
theoretical foundation for the experimentally
momentum (as do particles of mass).
based periodic table.
✓ The wave–particle duality of matter and energy
is observable only on the atomic scale.
✓ All physical and chemical behaviour of each
element in the periodic table is based on the
✓ According to the uncertainty principle, we electron configuration of its atoms.
cannot know simultaneously the exact position
and velocity of an electron.
✓ The elements in a group have similar outer
electron configurations and similar chemical
✓ The electron’s wave function (atomic orbital) is a properties.
mathematical description of the electron’s wave-
like motion in an atom.
✓ Atomic radius increases down a group and
decreases across a period.
✓ Each wave function is associated with one of the
atom’s allowed energy states.
✓ Across the transition series the atomic radius
remains approximately constant.
✓ An electron density plot and a radial probability
distribution plot show the electron occupies the
✓ The first ionization energy decreases down a
group and increases across a period.
space near the nucleus for a particular energy
level. ✓ Successive ionization energies show a largest
increase when inner core electrons are being
removed.

Review questions
1 Arrange the following atoms in order of increasing
atomic radius: W X

Al, P, C, K, Na
Y Z
2 The first electron affinity of the oxygen atom releases
141 kJ mol−1 of energy but the second electron
affinity requires an energy input of 844 kJ mol−1.
(a) Which element has the highest electron affinity?
Suggest an explanation for this observation.
(b) Which element has the largest radius?
3 The diagram represents a section of the periodic table, (c) Which element has the largest first ionization
with elements W, X, Y and Z marked. energy?
(d) Which element has the smallest first ionization
energy?
26 Unit 1 Module 1 Fundamentals in chemistry

4 Provide explanations for each of the following Answers to ITQs


observations.
1 mass = 160 g = 0.16 kg; velocity = 38.9 m s−1; so
(a) Peaks in first ionization energies occur with atoms
p = 6.2 kg m s−1; h = 6.63 × 10−34 m2 kg s−1
with atomic numbers 4, 7, 10, 18, 36.
(b) Elements with atomic numbers 9, 17, 35 have h 6.63 × 10−34
λ= = ≈ 1 × 10−34 m
large electron affinities whereas those with atomic p 6.2
numbers 10, 18, 36 have very small or zero 2 Both theories were preceded by ‘continuous’ theories:
electron affinities. one that matter is infinitely divisible and the other
that energy is infinitely divisible also.
5 Successive ionization energies for elements P, Q and R
are given in Table 2.4. 3 Cl < Na < Br < K
Table 2.4 Na and Cl are in the third period, n = 3, with Cl
Element 1st IE 2nd IE 3rd IE 4th IE 5th IE having the greater nuclear charge so the Cl atom is
X 786 1577 3229 4356 16080 smaller than Na atom (Cl < Na). K and Br are both in
Y 738 1450 7732 10550 13620 the fourth period, n = 4, with Br having the greater
Z 577 1816 2744 11580 15030 nuclear charge and the smaller radius (Br < K).
Both K and Br are larger than Na and Cl since their
(a) Where would each element would be found in the
outermost electrons are in a shell further from the
periodic table? Explain your answer.
nucleus.
(b) Given that all three elements are in the same
period, which of the three elements would have 4 (a) Na+
largest atomic radius? (b) Cl−
6 The sizes of the species Ne, F−, N3− and Na+ are Consider the electronic configuration of the ions:
represented by the spheres shown below. Match each Electronic Nuclear Number of
Ion
species with an appropriate sphere. Explain your configuration charge electrons
answer. Na+ 1s2 2s2 2p6 +11 10
Cl− 1s2 2s2 2p6 3s2 3p6 +17 18
O2− 2 2
1s  2s  2p 6
+8 10
A B C D
Na+ and O2− have the same electronic configuration
(are isoelectronic); however, Na+ has the greater
7 Plot and interpret a graph of ionization energy nuclear charge and so its electrons will experience
(kJ mol−1) on the y-axis against the number of a greater nuclear attraction than O2−. Na+ will be
electrons removed (x-axis) for the elements Li, C, O smaller than O2−. The outer electrons in the Cl− ion
and S. are in the n = 3 shell and so are further from the
nucleus than those of the Na+ and O2− ions, whose
8 Which of the following ions would lose an electron
outer electrons are in the n = 2 shell. The Cl− ion is
most easily?
therefore the largest of the three ions given.
S2−, Cl−, Ar, K+, Ca2+
5 In the gas phase there is little interaction between
9 Which of these atoms would have the largest 1st atoms and hence it is the best representation of an
ionization energy? isolated atom. If the atom was bonded to another (as
[Ne] 3s2 3p1, [Ne] 3s2 3p2, [Ne] 3s2 3p3, [Ne] 3s2 3p4, is the case for liquid or solid phases), then some of the
[Ar] 3d10 4s2 4p3 energy applied to the atom in the ionization process
would be absorbed in breaking bonds.
10 Place these elements in order of increasing ionization
energies?
Al, B, C, K, Na
Chapter 2 The quantum atom and the periodic table 27

6 P = [Ne] 3s2 3p3; P: ҘғҘҘҘ 9 The equations for the first and second electron affinity
of an atom X are:
S = [Ne] 3s2 3p4; S: ҘғҘғҘҘ
X + e− → X− EA1
The P atom has three 3p orbitals each containing an X− + e− → X2− EA2
unpaired electron arranged with parallel spins. This
The second electron affinity involves adding an
arrangement of electrons minimizes electron–electron
electron to a negatively charged ion. There will be
repulsions among the electrons. In the S atom one of
significant electron–electron repulsions to overcome
the p orbitals contains a pair of electrons with opposite
so energy would have be input in order to force the
spins. These electrons sharing the same region of
electron on the negatively charged ion.
space will experience added repulsion from each other
in addition to that experienced from electrons in the
other orbitals. Removing an electron from the S atom
Answers to Review questions
on ionization results in a reduction of the electron– 1 C, P, Al, Na, K
electron repulsions hence the process is favourable 2 Second electron added to a negatively charged O− ion
and hence the lower ionization energy of S. so there is increased electron–electron repulsions
7 Atom I, since after the removal of the first two making it harder to add an electron.
electrons the species formed has a noble gas 3 (a) X
configuration. (b) Y
I (1s2 2s2 2p6 3s2) → I+ (1s2 2s2 2p6 3s1) + e−; (c) X
electron lost is from 3s IE1 (d) Y
I+ (1s2 2s2 2p6 3s1) → I2+ (1s2 2s2 2p6) + e−; 5 (a) X is Group IV (14); Y is Group II (2),
electron lost is from 3s IE2 Z is Group III (13)
I2+ (1s2 2s2 2p6) → I3+ (1s2 2s2 2p5) + e−; (b) X
electron lost is from 2p IE3
6 A = N3−; B = F−; C = Ne; D = Na+
8 Since N is smaller and has a greater nuclear charge
than C, we would expect N to have a greater electron 8 S2−
affinity than C. The opposite is observed, which 9 [Ne] 3s2 3p3
suggests that we need to consider other factors. One
10 C, B, Al, Na, K
such factor is the electron–electron repulsions in the
resulting ions.
The electron configurations of the neutral and charged
ions of each atom are as follows:
C ([He] 2s2 2p2) + e− → C− ([He] 2s2 2p3) EA1
Ҙғ Ҙ Ҙ Ҙғ Ҙ Ҙ Ҙ
N ([He] 2s2 2p3) + e− → N− ([He] 2s2 2p4) EA1
Ҙғ Ҙ Ҙ Ҙ Ҙғ Ҙғ Ҙ Ҙ
Carbon has an empty p orbital which can
accommodate an additional electron with an opposite
spin (reducing repulsive effects). Nitrogen has an
unpaired electron in each of its p orbitals so an
additional electron would have to be accommodated
in an orbital which is already occupied. This electron
would experience increased repulsions from the
electrons already present which offsets the increased
nuclear attraction due to its greater nuclear charge.
The net result of this is the nitrogen atom has a lower
electron affinity than the carbon atom.
28

Chapter 3
Radioactivity
Learning objectives
■ Appreciate that some atomic nuclei are unstable.
■ Understand the words ‘isotope’ and ‘nuclide’.
■ Distinguish between α, β and γ radiations.
■ Explain the origins of α, β and γ radiations.
■ Write symbols for sub-atomic particles and nuclides.
■ Write simple nuclear equations.
■ Describe selected uses of radioactive nuclides.

Introduction: the alchemists’ dream


In Europe, in the Middle Ages, chemists (known then forth, rather like children playing together, throwing and
as alchemists) tried to invent a magical potion that they catching a ball. As long as the numbers of good throwers and
called the ‘philosopher’s stone’. This potion would change good catchers roughly balance, the group stays together.
base metals, such as iron, into gold and also give the gift of Similarly, in nuclei, as long as the neutron : proton ratio
eternal life. They amassed a huge store of what we would does not depart too far from 1, the nucleus is likely to be
now call ‘industrial chemistry’ and a fair knowledge of stable – though there are other factors to take into account.
medicine, but they failed to find the philosopher’s stone. The neutron  :  proton ratio is close to 1  :  1 up to about
Dalton’s theory (see page 3, Chapter 1) seemed to explain Z = 20, then increases slowly up to about 1.6 : 1 (Figure 3.1).
why they failed: atoms, according to Dalton’s theory,
120
were immutable and indivisible. Both Bohr’s theory and
Thomson’s ‘plum pudding’ model of the atom also offered 110

no hint that atoms could change. However, Rutherford’s band of stability


100
nuclear model put matters in a different light, as well as
raising some more questions. 90

How can several positively charged particles possibly exist 80


N=Z
Number of neutrons, N

so close to each other in the nucleus of an atom? The 70


electrostatic force pushing them apart, which doubles in
60
strength as the distance between the particles is halved,
is enormous. Some hitherto unknown force must oppose 50

that repulsion and make the nucleus stable. This force is


40
called simply the strong force.
30
The strong force is one of the four fundamental forces of
nature: the others are the electromagnetic force, gravity 20

and the ‘weak force’. The strong force operates between 10


quarks, the particles which themselves make up protons
0
and neutrons. All these forces are non-contact forces. 0 10 20 30 40 50 60 70 80 90
Number of protons, Z
As well as protons, the nucleus also contains neutrons. The
strong force can be thought of as operating between the Figure 3.1 Ratio of protons to neutrons in stable nuclei.
protons and the neutrons, transferring energy back and
Chapter 3 Radioactivity 29

Nuclear transitions The alchemists’ dream of transforming one element into


another has been realized. The atomic number of the
Isotopes are atoms of any element X which have the same product atom is one greater than the original atom. It is an
proton number but different numbers of neutrons (see atom of a different element. The element has moved along
page 2, Chapter 1). You should note that the word ‘isotope’ one place in the periodic table.
can only be used if you say which element you are talking
about. If you don’t give the name of the element then the α emission
word to use is nuclide. So we may speak of ‘the isotopes of
What about an atom that has too few neutrons to be
chlorine’ but ‘nuclides with different numbers of neutrons’.
stable? The nearest electrons are too far away from the
For nuclear stability, even numbers of neutrons are nucleus to be captured, so the nucleus cannot change by
preferred to odd, and the same applies to the number of forming a neutron from a proton and an electron. Rather
protons, and even numbers of both are best of all (Table than ejecting a proton, the nucleus can eject a helium
3.1). However, when the n  :  p ratio is within allowable nucleus, 42 He, which is a very stable particle. This type of
limits and no other rules are broken, the nucleus is stable. decay is confined to heavier nuclei. Lighter nuclei decay by
Table 3.1 Numbers of stable nuclides with odd and even
emitting antimatter. (Antimatter is a topic that is outside
numbers of protons and neutrons the scope of your course but if you want to know more,
Z N Number of stable nuclides look up ‘positron’ on the web!)
odd odd 4 Emitting a helium nucleus reduces the atomic number
odd even 50 by two units so the new element is two places earlier in
even odd 57 the periodic table. The helium nuclei that are ejected are
even even 168 called alpha particles (α particles). Even though both
the proton number and the neutron number have gone
Stable nuclides are shown within the green area in Figure down by two, the n : p ratio will have increased.
3.1. Outside these limits, the nucleus is unstable (it contains
too much inherent energy) and in the manner of all hyper- Nuclear equations
energetic systems, changes towards a more stable state by
The changes to atoms and molecules in a chemical reaction
losing some energy. This change is called a decay.
can be recorded in a chemical equation. In the same way,
A proton has a mass of approximately 1 amu (atomic mass the nuclei and sub-atomic particles in a nuclear reaction
mass
unit) and a charge of +1. Using the convention charge X, can be recorded in a nuclear equation. The same rules
1
we write a proton a 1 p. Similarly, we write a neutron apply: the total mass and the total charge must be the same
as 10 n and an electron as −10 e. We can think of a neutron as on both sides.
a proton plus an electron. This can be written as a nuclear
equation:
1
Worked example 3.1
0
n = 11p + –10e
A platinum nucleus with relative atomic mass 195 loses a
Q β particle to form a nucleus of gold. Write an equation to
β emission show this change.
If a nucleus has too many neutrons to be stable, then one of
(i) Look up the values of Z for platinum (Pt) and gold (Au). They
them can change to a proton plus an electron. The neutron A are 78 and 79, respectively.
number goes down by one and the proton number goes
(ii) The new nucleus of gold must also have A = 195 because
up by one. The n : p ratio has changed towards the stable a beta particle has no mass. You can now write symbols for
value. However, electrons cannot exist inside the nucleus, this nuclear reaction:
so the electron, the second product of the nuclear change, 195 195
78
Pt 79
Au + –10e
is ejected. The ejected electrons are called beta rays (β
rays), but you should use the term beta particle if you (iii) Check that mass (195 = 195 + 0) and charge
are talking about just one. (78 = 79 + −1) both balance. This is fine.

ITQ 1 Which element would you need to start with in order to ITQ 2 Why is the helium nucleus stable?
transform it into gold by β emission?
30 Unit 1 Module 1 Fundamentals in chemistry

Radioactive decay Properties of α, β and γ rays


Radioactive decay is a first-order reaction (see page 90, These three types of radiation are all used to our advantage,
Chapter 9). The rate of radioactive decay is unaffected by although they can also be harmful. Table 3.2 shows some
changes in temperature, pressure or chemical environment. of their important properties.
One feature of first-order reactions is that they have a
Table 3.2 Properties of α, β and γ rays
fixed half-life (t 12 ). This means that the time taken for
Alpha Beta Gamma
the amount of a material to halve (that is, change from 1
1 1 mostly as a
to 2 to 4 and so on) is constant. Half-lives of radioactive Character
particle
particle or ray mostly as rays
nuclides vary from fractions of a second (e.g. 315Po, t 12 Relative mass
4 approx. 1/2000 almost zero
= 3 × 10−5 s) to billions of years (e.g. 238U, t 12 = 1 × 1011 / amu
penetrates skin, thin penetrates lead
years). Each nuclide has its own characteristic half-life. Penetrating stopped by skin or
sheets of aluminium sheet, human body
Some nuclides with very long half-lives are found in the power tissue paper
or Perspex or concrete
environment around us. They give rise to the low levels Ionizing power high medium almost zero
of background radiation that surrounds us constantly –
and has done since the beginning of time. Problems caused by radiation
Energy changes in radioactive decay If sufficient energy is emitted in a small length of time, the
outcome can be an explosion. The most famous examples
We sometimes assume that protons and neutrons have a
are the two bombs dropped on Japan in August 1945 to
mass of exactly 1 amu and that electrons have no mass at
bring an end to the Second World War in the Pacific.
all. This is only an approximation to the truth, although
it does work well much of the time. In fact, neutrons are More recent examples of the danger of radiation can be seen
a little heavier than protons and electrons do have some following the explosion at the Chernobyl power station
mass. (April 1986) and the nuclear meltdown in the Japanese
nuclear reactor at Fukushima (March 2011). In both of
If we use Einstein’s famous equation, E = mc2, we see that
these the danger arose from highly active radionuclides
mass (given by m) and energy (given by E) are really the
scattered in the explosions rather than the disruptive
same thing. This means that when we say that mass is
power of the explosions themselves.
conserved in a nuclear change, we should really say that
the total of (mass + energy) is conserved. For example, in The harmful effects of these radiations come mainly from
the change from a neutron to a proton plus an electron, their ability to ionize atoms. If ionization happens within
a tiny amount of mass, less than one thousandth of an a living cell there is the risk that the damage will not be
atomic mass unit, is lost: this ‘lost’ mass appears as energy repaired, and therefore the cell ceases to function. If
– the electron is ejected at very high speed. enough cells are damaged, illness or even death can be the
result. This is known as radiation sickness.
In many other changes, the final nucleus (the daughter
nucleus) is left in an excited (high-energy) state. The If the damage is in the gametes (i.e. in a sperm or an egg),
excess energy is then emitted as electromagnetic radiation then damaged DNA can be passed down through the
with wavelengths roughly 100 times those of X-rays. These generations. Inherited genetic mutations are not often seen
radiations are called gamma rays (γ rays). We do not in humans because the individual damaged sperm or ovum
include them in equations of nuclear change because they must be involved in reproduction, and also because most
carry neither mass nor charge. mutations produced in this way are in recessive genes, not
dominant genes.
In the plant world, however, radiation-induced changes
ITQ 3 A nucleus has Z = 86 and N = 132. are more common. For example, new varieties of food
(a) What is its n : p ratio?
crops such as rice and the ornamental Chrysanthemum have
(b) What is the new n : p ratio after an alpha particle is emitted?
(c) What were the two nuclides? been produced by gamma irradiation. The process is called
‘mutation breeding’ and can be beneficial.

ITQ 4 Tritium is an isotope of hydrogen and it has two neutrons


in its nucleus. Write the nuclear equation describing the decay of ITQ 5 Write the nuclear equation for the transition mentioned in
tritium (3H) to helium-3 (3He). ITQ 3.
Chapter 3 Radioactivity 31

Uses of radioisotopes enters the detector the ionization is interrupted, the current
is reduced, and an alarm sounds.
Radiotherapy
The ionizing effect of radiation can be used to kill cancer β sources
cells in the body. This is known as ‘radiotherapy’. Either Beta sources are valuable as tracers, especially in medicine.
a beam of radiation is targeted onto the cancer so that Some nuclides become concentrated at particular sites in
surrounding tissue is not so much affected, or tiny ‘seeds’ the body. An example is 131I (iodine), which gathers in the
of nuclides producing short-range radiations are implanted thyroid gland. The distribution of the nuclide in the gland
directly into the tumour. X-rays and γ-rays are used, as are can be detected because it undergoes β decay, and this
protons and β particles. helps in the diagnosis of problems.
By incorporating an active nuclide into a molecule and
Fission reactions
then tracing its pathway through subsequent reactions, we
In the nuclear reactions called fission reactions (so-called can get information about the mechanism of the reactions.
because large nuclei split into two or more smaller
Because β rays have greater penetrating power than α
fragments), large quantities of energy are released. Fission
particles, they can be used to monitor and control the
reactions are triggered by the absorption of neutrons
thickness of sheet material produced in a rolling mill. A
into susceptible nuclei such as 238U. If this absorption
of neutrons is uncontrolled and the mass of fissionable source such as 37Cs (caesium) is held on one side of the
sheet and a detector is positioned on the other side. If the
material is sufficient, then an explosion is the result. But
sheet produced is too thick the signal is reduced and more
neutrons are easily controlled, and so the release of energy
pressure is applied to the rollers producing the sheet. If
can be slowed down to make a useful, safe, power source. In
the sheet is too thin, the signal will be increased and the
many countries, nuclear power stations provide significant
pressure needs to be reduced.
proportions of the total energy supply. At present there are
no nuclear power stations in the Caribbean region, though Beta radiation can be used to date ancient organic material.
they are common in the USA. Atmospheric CO2 contains trace amounts of the β emitter
14
C. 14C is photosynthesized in the same way as 12C,
In most cases the heat energy released by the fission
becoming part of living material. When the organism dies,
reaction is used to boil water, and then the steam is used
the 14C is no longer replaced. The amount in the organism
to drive electricity generators. The downside of the process
decays, with a half-life of 5370 years. By measuring the
is that it is hard to dispose safely of the radioactive waste
beta activity of an ancient material and comparing it to the
from the power station.
activity expected in a living sample, the age of the material
α particles can be worked out. The method is used for carbon-
containing materials with ages up to about 60 000 years
The decay of nuclides releasing α particles is used in
and is commonly used in archaeological investigations.
batteries that must remain unattended for long periods.
Such batteries are used in spacecraft or heart pacemakers. Gamma rays
238
Pu (plutonium) decays in this way. Some of the energy
Gamma radiation is highly penetrating and affects
released in the decay appears as heat, which is used to warm
photographic film in the same way as X-rays. It is used
one side of a bank of thermocouples. The thermocouples
in industry to check for flaws in heavy components such
then produce an electrical output. The output from 1 g of
as remote pipelines. The source of the rays is often 60Co
plutonium is about 0.5 W.
(cobalt): such a source can be made portable and can be
Why is such a system useful? The α particles are easily used in locations where no power is available for X-ray
absorbed by thin shielding and therefore present no health machines.
hazard and the rate of decay of 238Pu is slow (t 12 = 88 years)
In medicine, gamma rays can be used to destroy cancer
so the batteries have a long life.
cells, gamma radiation can be used to sterilize pre-packed
A more familiar use is in smoke detectors. Here a tiny surgical instruments, and has been used to kill the pupae
amount of 241Am (americium) ionizes the air between two of the cotton boll-weevil, which is a serious pest in the
electrodes, allowing a tiny current to pass. When smoke American cotton-growing industry.
32 Unit 1 Module 1 Fundamentals in chemistry

Summary
✓ When an atomic nucleus changes into a different
nucleus, the process is called radioactivity.
✓ In a radioactive change the nucleus may emit
alpha, beta and or gamma rays.
✓ Each radioactive decay has a characteristic half-
life.
✓ Alpha, beta and gamma rays differ significantly
in penetrating power.
✓ Atomic radiation can be dangerous but it can
also be highly beneficial.

Review questions Answers to ITQs


1 (a) Explain what is meant by the statement ‘Chlorine 1 Gold has Z = 79. The element with Z = 78 is platinum.
has two isotopes, chlorine-35 and chlorine-37’. 2 The helium nucleus contains even numbers of protons
(b) Another isotope of chlorine, chlorine-38, can be (2) and neutrons (2) and its n : p ratio is 1.
made but it has a half-life of 37 minutes.
(i) What is meant by the term ‘half-life’? 3 (a) Original n : p ratio is 1.535 : 1.
(ii) Why does this isotope of chlorine not exist in (b) The n : p ratio is 1.548 : 1. Not a great change but
nature? a move in the required direction.
(c) The original nuclide was 21886 Rn, which become
2 (a) Atoms of the nuclide strontium-88 are stable. 214
84 Po.
Atoms of its isotope strontium-89 are radioactive.
What difference between the nuclei of the two 4 3
1H → 32 He + 0
−1 e

makes the heavier atom unstable? 5 218


86 Rn → 214 4
84 Po + 2 He
(b) The heavier isotope has a half-life of 50 days. It
emits ˚ particles.
(i) What is a ˚ particle?
(ii) Atomic nuclei contain only protons and
neutrons. Explain the origin of the ˚ particle.
(iii) Why does emitting the ˚ particles make the
strontium-89 atoms more stable?
(iv) How long would it take 15/16 of a sample of
strontium-89 to decay?
33

Chapter 4
Chemical bonding
Learning objectives
■ Explain the origin of the forces which act as chemical bonds.
■ Describe ionic, covalent, hydrogen, van der Waals and metallic bonds.
■ Explain the ways in which some physical properties of materials are
related to the bonds that they contain.

Introduction One driving force behind the formation of stable


In Chapter 2 we considered the concepts of ionization of molecules is the attainment of minimum potential
the elements, looking at ionization energy and electron energy.
affinity, and we have also already discussed atomic size. In
this chapter, you will see the role that these concepts play Types of chemical bond
in bond formation.
We need to consider five types of chemical bonds:
Formation of bonds ■ ionic bonding;
■ covalent bonding;
Chemical bonds are forces that hold atoms or ions together
■ hydrogen bonding;
in a compound. Without the formation of chemical bonds
we would have only naturally occurring ‘free’ elements ■ metallic bonding;
rather than the millions of different molecules that exist. In ■ van der Waals forces.
nature ‘free’ elements are rarely found. Instead, we have Bonding mechanisms need to explain a range of situations,
compounds containing elements bonded to each other or bearing in mind that bond formation is directly related to
to other elements. energy changes.
It is therefore clear that in the natural world a combined ■ Some substances, for example sodium chloride, NaCl,
state is preferred. Why is this? have bonds between oppositely charged ions.
We say that the combined state is ‘more stable’ and this ■ In a substance such as water, H2O, the bonds are
turns out to mean ‘a state of lower potential energy’. between two apparently neutral atoms.
■ Water boils at a temperature well above that which its
Think about the process of bringing atoms together:
molecular mass would suggest.
■ the positively charged nucleus of each atom attracts
■ Metals conduct heat and electricity.
its own negatively charged electrons, as well as the
■ Noble gas atoms, normally existing in isolation, do
electrons of nearby atoms
stick together at low enough temperatures.
■ the positively charged nuclei will repel each other
■ the electrons of the atoms will repel each other.

In other words, when atoms approach each other, there is a


set of attractive and repulsive interactions. If the attractive
interactions exceed the repulsive ones, then the atoms
combine to form a stable particle of lower potential energy. ITQ 1 Suggest why the cold water in a kettle does not
The atoms are said to have formed a chemical bond. spontaneously come to its boiling point.
34 Unit 1 Module 1 Fundamentals in chemistry

Bond formation and energy changes the process of ionization can occur through electron
transfer and the charged species once formed will attract
The likelihood of an ionic compound being formed is each other to form the crystal. These steps are summarized
related to the stability of the compound that is formed. below, and values for their enthalpy changes are given.
We can get an indication of the stability of the compound 1 1
from its standard enthalpy of formation (ΔH f ). If
Step 1 2 Br2(l) → 2 Br2(g) ΔH = +15.0 kJ
1
ΔH f is negative, the formation reaction is exothermic Step 2 2 Br2(g) → Br(g) ΔH = +96.6 kJ
(heat is given out), the compound formed is stable and Step 3 K(s) → K(g) ΔH = +89.9 kJ
likely to be formed.
Step 4 Br(g) + e → Br (g) − −
ΔH = −341.4 kJ
As an example, let’s look at the formation of potassium
bromide, KBr. Step 5 K(g) → K+(g) + e− ΔH = +418.4 kJ

Combining solid potassium with liquid bromine (Br2) Total so far: ΔH = +278.5 kJ
results in a violent reaction. Solid KBr is produced, as well As we saw above:
as a great amount of heat. The equation for this reaction is: 1
K(s) + 2 Br2(l) → KBr(s) ΔH = −389.9 kJ mol−1
1
K(s) + 2 Br2(l) → KBr(s) ΔH f = −389.9 kJ mol−1 Therefore, the difference must be due to the formation of
You are probably asking ‘Why is the formation exothermic’? the solid lattice:
‘Why is the formation of KBr so favourable?’ ‘Does it arise Step 6 K+(g) + Br−(g) → KBr(s) ΔH = −668.4 kJ mol−1
from the transfer of electrons from K to Br?’
The enthalpy change for Step 4 is the electron affinity and
If we look at the enthalpy change for the electron transfer for Step 5 is the ionization energy. These enthalpy changes
process only, we will see that this is not an exothermic are discussed in more detail in Chapter 8.
process:
Most of the steps, except 4 and 6 above, are endothermic
K(g) + Br(g) → K+(g) + Br−(g) ΔHf = +77 kJ mol−1 processes. This means that they require an input of energy.
Note that separated atoms are considered to be similar to If you sum all the steps up to the formation of the gaseous
gaseous phase atoms, hence the (g) representation. ion (Steps 1–5), you obtain a value of ΔH = +278.5 kJ.
Although ΔHf cannot be measured directly, it can be The enthalpy of formation is the sum of all the enthalpy
calculated using other known enthalpy values – as you will changes for the six steps listed.
see later.
Clearly, the above endothermic reaction does not give the
complete story. However, we can consider all the steps that
+89.9
might be involved in the reaction. If the enthalpy changes
step 5
for these steps are known, then by applying Hess’s law (see
page 81, Chapter 8), the sum of the enthalpies of these step 3 +418.4

individual steps should be equal to the formation enthalpy +96.6 step 4


–341.4
of KBr. The application of Hess’s law to thermochemical
step 2
analysis cycles is called a Born–Haber cycle (see page 84, +15.0
initial state step 1
Chapter 8). step 6

Let us look at some of the possible steps.


–668.4
Before any atom of potassium can combine with any atom
of bromine, they must first be separated from other atoms cumulative energy changes for the reaction:
to which they are bonded. That is, in the solid metallic K K(s) + 1
Br 2 (l) KBr(s)
2
there are several K atoms bonded to each other and in the
liquid Br2 there are Br2 molecules bonded to each other
and Br atoms bonded together within them. One way of
final state –389.9
separating the atomic interactions in each reactant is by
taking them to a gas phase. Once the atoms are separated,
Chapter 4 Chemical bonding 35

Since the formation of gaseous (free) ions from solid K and When sodium solid burns in chlorine gas the white
liquid Br2 is an overall endothermic process, it is the last crystalline solid sodium chloride is produced. This
step (step 6), where the ions attract each other to form the compound contains positively charged sodium ions and
lattice (crystalline network), that makes the overall process negatively charged chloride ions. Sodium has lost its 3s
exothermic. electron to the chlorine atom.
Thus the major contributing factor to the stability of KBr is Na → Na+ + e−
the strong force of attraction between the ions that give rise 1s2 2s2 2p6 3s1 1s2 2s2 2p6
to the formation of the crystal. The energy change associated Cl + e− → Cl−
with the formation of the solid crystal from these gaseous 1s  2s  2p6 3s2 3p5
2 2
1s  2s  2p6 3s2 3p6
2 2
ions is referred to as the lattice energy. If this is large and
positive then the compound will be stable. If it is small it Notice that for both ions the electron configuration
may not be sufficient to supply the energy needed to reach acquired after the electron transfer is that of a noble gas,
the intermediate state and so the compound is unstable. that of neon in the case of sodium and that of argon in the
case of chlorine.
Similar arguments can be applied to the formation of
any type of bond. If the overall energy change between A charged ion can interact with another ion approaching
reactants and products is negative (that is to say, the from any direction, and so the attraction between the
reaction is exothermic), then the products are favoured oppositely charged Na+ and Cl− ions gives rise to a three-
over the reactants. This is frequently the most important dimensional structure or lattice (Figure 4.2).
factor, but it is not the only one. a b

■ Ammonium nitrate dissolves readily in water but the


reaction is endothermic.
■ Citric acid reacts with sodium bicarbonate, but the
reaction is endothermic.
■ Solid barium hydroxide reacts with solid ammonium
nitrate to form an intensely cold slurry.
Something must be over-riding the energy change to make
these reactions proceed. The ‘something’ is a change in
Figure 4.2 (a) The 3D structure of solid sodium chloride. (b) This
entropy, but this topic is outside the scope of this book. structure shows the positions of the ion nuclei.

Ionic bonding A crystal of sodium chloride does not consist of one single
sodium ion bonded to one chloride ion. On the contrary,
Metal atoms have between one and three outer electrons. it consists of a lattice of several positively charged sodium
Non-metals usually have one or two unfilled gaps in theirs. ions surrounded by and attracted simultaneously to
When a metal atom transfers an electron to a non-metal several negatively charged chloride ions. The formula
atom, the metal acquires a net positive charge and the NaCl gives the ratio of Na+ to Cl− that exists within the
non-metal a net negative charge. These oppositely charged lattice. A crystal of NaCl can therefore be regarded as a
ions will attract each other. It is the electrostatic force of giant molecule of the compound.
attraction between the ions that constitutes a bond. This
type of bond is the ionic bond.
As an example, we will look at sodium chloride, NaCl Covalent bonding
(Figure 4.1). Note that the positive ion is smaller than its If two elements are very similar in their outer electron
parent atom. The negative ion is larger than its parent ion. configurations, or if achieving a noble gas configuration
would produce a high ionic charge (e.g. C4+), atoms can
produce stable compounds without ionization. Water
+ –
Na Cl Na Cl provides an example.

ITQ 2 Why would you expect a stronger ionic bond between


Figure 4.1 The electrostatic nature of the ionic bond. lithium and fluorine than between sodium and chlorine?
36 Unit 1 Module 1 Fundamentals in chemistry

Oxygen atoms have two vacant places in their 2p shell: the


electron repulsion
electron structure is 1s2 2s2 2p4. Because they are mutually
repulsive, the p electrons are arranged as px2 py1 pz1.
A hydrogen atom has the electron structure 1s1. If a

Energy
nuclear repulsion
hydrogen atom is moved progressively towards an oxygen
atom in the direction of either the py or the pz electron,
it will at first be repelled (electron/electron interaction).
However, as the distance between the nuclei decreases bond position
a point is reached where this repulsion is balanced by
Particle separation
the two nucleus-to-electron attractive forces. Once this
equilibrium is achieved, changing the interatomic distance Figure 4.3 Energy changes in covalent bond formation.
either way needs an input of energy. The balance point is Py Pz
the position of least potential energy, which means that a
chemical bond has been formed (Figure 4.3). This type of
bond is a covalent bond.
Px
Remember: bond formation releases energy: bond
rupture needs energy input.

Although no ionization is involved, the covalent bond, like


the ionic bond, relies on electrostatic forces. The electron Figure 4.4 Hybrid orbitals in the carbon atom. The s orbital
of the O atom in the O–H bond is now attracted to both the contains two electrons, the py and the px orbitals one each. The
oxygen nucleus and the nucleus of the H atom. Similarly pz orbital is empty.

the electron from the H atom is attracted to the nucleus and produce the same total number (four) of equivalent
of the O atom. The pair of electrons acts like the jam in a orbitals. Since there are four electrons, one electron will
sandwich, holding the two nuclei together. exist in each of these new orbitals. They are called hybrid
orbitals and since these were made up from one s orbital
The covalent bond always comprises a pair of electrons. and three p orbitals, they are called sp3 hybrids.
We can show a covalent bond by using × as an electron.
Then the reaction H + H → H2 is shown as When a carbon atom combines with hydrogen it therefore
needs four hydrogen atoms, so that each orbital contains
H + H H H
+

++

a pair of electrons. When


+

To show which atom originally contained each electron we draw the ‘dot-and-cross’ H
we can use × and •: diagram of the bonds we
H C H
For example, the structure do not try to draw in 3D.
of the ammonia (NH3) Instead we imagine the H
H N H
molecule becomes structure flattened onto the Figure 4.5 The ‘dot-and-cross’
page, as shown in Figure 4.5. structure of CH4, methane.
This is called a ‘dot-and-cross’
diagram. H Although a covalent bond is usually formed using one
electron from each combining atom, it is possible for an
atom with an unused pair of electrons (a lone pair) to
Sometimes a low energy state can be obtained if orbitals (i.e. bond with an atom that has an empty electron shell. The
energy levels) co-operate with each other. For example, simplest example is the combination of ammonia with
the electron structure of carbon is 1s2 2s2 2p2. Figure 4.4 hydrogen ions:
shows how the electrons are distributed. NH3 + H+ → NH4+
These electrons all repel each other. To reach a state of In this reaction the nitrogen atom has a lone pair of
low energy they must be as far apart from each other as electrons (2p2) whereas the hydrogen ion has an empty
possible. This happens if one electron is at each point of shell (1s0). The effect is exactly the same, but the bond is
a tetrahedral pyramid surrounding the atom. For this to sometimes called the dative covalent bond since both
happen the original three p orbitals and the s orbital combine electrons are ‘donated’ by the one atom.
Chapter 4 Chemical bonding 37

In the formation of an Each molecule of water is held together by two covalent


H
ionic bond, electrons dative O–H bonds. Oxygen, however, has a greater capacity for
bond
are transferred from one attracting electrons to its nucleus than does hydrogen. On
atom to another. For the Pauling scale of electronegativity (see Chapter 2, page
H N H covalent bond formation 23), oxygen has the value 3.5 but hydrogen is only 2.1.
electrons are controlled The effect of this is that the pair of electrons making up
by the nuclei of both each O–H bond are not central between the nuclei, but
atoms simultaneously are displaced toward the oxygen. This in turn means
H
– often referred to as that each molecule has an electric dipole – a small but
‘sharing’ of electrons. The significant separation of electric charge. You can think of
Figure 4.6 Electron structure of
the ammonium ion NH4+. The ‘×’
ionic and covalent models it as a covalent bond with a small degree of ionic character
electrons come from the nitrogen of bonding represent the (Figure 4.9).
atom and the ‘•’ electrons come extremes of electron –
from the hydrogen atoms. transfer and electron O
+ +
H H
sharing. Most actual bonds fall somewhere between these –

+
O +
two extremes. A covalent bond between two particles of H H
different electronegativity (for example carbon and oxygen,
Figure 4.9 Hydrogen bonds in water, showing the polarity.
as in the carboxylate ion –COO−) inevitably means that in
the C–O bond the bonding pair lies nearer to the nucleus of Although the molecules in liquid water are in constant
the oxygen atom, giving it a small negative charge (δ−) and random motion, any two molecules will be, for a short
leaving a small positive charge (δ+) on the carbon atom. period, close to each other. If they are oriented as shown in
Figure 4.10, an electrostatic attractive force exists between
The hydrogen bond them. It is only about 10% the strength of either an ionic
bond or a covalent bond. However, it is strong enough that,
Liquid water has two features which appear anomalous. for the short time that the molecules are close together, the
■ Its melting point and boiling point are much higher effective molecular mass of the molecule is greater than
than its molecular mass would suggest (Figure 4.7). when the molecules are solitary.
■ Its density does not change regularly as its temperature The effect need not be restricted to two molecules. It is
falls, especially around the freezing point (Figure 4.8). restricted to an interaction between the positively charged
hydrogen and a lone pair on the oxygen, so one water
100
molecule can potentially form four hydrogen bonds at the
Boiling point / ˚C

same time. The strength of the hydrogen bond is greater


0
than might be thought because the small size of the
polarized H atom allows close approach of the polarized O
–100
atom (Figure 4.10). The effect is electrostatic and therefore
obeys the inverse square law.
–200
CH4 NH3 H2O HF

Figure 4.7 Boiling points of water and other molecules of similar


molecular mass. Water is very much the ‘odd one out’.
198 pm
1.000
H
96 pm
Density / g cm –3

0.99 O
H
0.98
Figure 4.10 The lengths of the covalent O–H bond (96 pm) and
0.97 the O...H hydrogen bond (198 pm).

0.96
0 4 20 40 60 80
Temperature / ˚C
ITQ 3 Draw a diagram showing the electron structure of the
Figure 4.8 The density of water does not change regularly as its hydrated proton H3O+.
temperature falls.
38 Unit 1 Module 1 Fundamentals in chemistry

Hydrogen bonds are formed between molecules which


contain polarizable hydrogen atoms and those which have
an atom with higher electronegativity (such as oxygen,
nitrogen or fluorine) that have at least one lone pair R
(Figure 4.11). Hydrogen fluoride fits these criteria but
R
each molecule can only form two H-bonds. Therefore, the
increase in boiling point is not so pronounced as in water.
100 H2O
80
60 H bond R
Boiling point / ˚C

40
HF
20 H2Te
0
SbH3 R
–20 H2Se
NH3
–40 H2S Hl
–60 AsH3 R
–80 HCl HBr
PH 3
–100
Period 2 Period 3 Period 4 Period 5

Figure 4.11 Hydrogen bonding in NH3, H2O and HF means that


the boiling points for these molecules are higher than expected
as compared with similar molecules. Figure 4.12 Hydrogen bonding is important in giving proteins
their 3D structure.
The formation of hydrogen bonds also accounts for the
anomalous density changes in water as it is cooled. As materials, although this is not an absolute rule. For
the temperature falls, thermal agitation becomes less and example, silver is an excellent electrical conductor but
more H…O interactions are effective in holding molecules its thermal conductivity is less than that of diamond, an
together. The molecules become closer together, as we electrical insulator.
would expect. But at 4 °C the equilibrium between their Sodium can be taken as an example of a substance that has
formation and break up tips in favour of formation, and metallic bonding. Sodium has the electron structure 1s2 2s2
the H-bonded state begins to predominate. Networks 2p6 3s1. The 1s, 2s and 2p electrons are strongly bound to
of water molecules mimicking fragments of ice begin to the nucleus and take no part in the metallic bond. When
have transient existence, and the structure is one which two sodium atoms come together, their 3s atomic orbitals
occupies more volume than the normal liquid state. Hence fuse into one molecular orbital. (See page 47 for more
as the temperature falls towards 0 °C, the structure of the about this concept.) The total number of orbitals cannot
‘liquid’ becomes more and more open, meaning that its change so a second orbital is created at a higher energy
density falls. 4 °C is the temperature at which water has its level.
maximum density, 999.8395 kg m−3. single orbitals

Hydrogen bonds can form between different molecular a 3s 3s


species, such as water and an alcohol or water and a
sugar, or within a complex molecule such as a protein or molecular orbitals
DNA. The release of energy as H-bonds form is the factor b
controlling the solubility of alcohols and sugars in water.
The H-bonding within a protein or DNA molecule may
Figure 4.13 3s orbitals for sodium. (a) Two orbitals form separate
lock the conformation and hence the shape of the molecule atoms; (b) two atoms forming a molecular orbital.
(Figure 4.12).
As more sodium atoms are added they add they form a
second, almost identical molecular orbital. No two electrons
The metallic bond
can have exactly the same energy, so this orbital is at a
True metals have properties that cannot be explained on
the basis of covalent, ionic or hydrogen bonding. They
conduct electricity very well in the solid state, obeying ITQ 4 The structure of glucose can be represented as
Ohm’s law. They conduct heat better than most other OHC–(H–C–OH)4–CH2OH. Why is it so soluble in water?
Chapter 4 Chemical bonding 39

very slightly different level. When many atoms are added, forces but the intramolecular covalent bonds within the
the energy levels of all the molecular orbitals fuse together naphthalene do not break even at its boiling point of 218 °C.
into a ‘band’ extending across the whole of the metal. The There are three types of attractive force between molecules.
higher-level orbitals do the same. They are generally taken together and called van der Waals
The upper level and lower level bands are called the forces. You may also find the second and third types called
‘conduction band’ and the ‘valence band’ (Figure 4.14). ‘London’ forces after Fritz London, who first suggested
them. The three types are:
conduction ■ dipole–dipole interactions;
band
■ dipole–induced dipole interactions;

overlap ■ induced dipole–induced dipole interactions.


Electron energy

band gap Dipole–dipole interactions


We have already seen one example of dipole–dipole
interactions in the hydrogen bond. But very few molecules
valance
are electrically neutral everywhere, unless neighbouring
band atoms have closely similar electronegativities.
For example, a hydrocarbon chain such as butane, C4H10,
metal semiconductor insulator
is scarcely polar. However, 1-fluorobutane contains a C–F
Figure 4.14 Valence and conduction bands in metals, bond and is significantly polar, with the fluorine atom
semiconductors and insulators. carrying a small negative charge (written δ− to distinguish
In a metal the two bands overlap and so electrons from the it from a whole ‘one-electron’ charge). The corresponding
valence band can enter the conduction band. This extends positive charge is distributed over the nearby atoms. Table
across the whole of the metal. Electrons in it are free from 4.1 gives some Pauling electronegativites. Note how similar
their original nuclei and are free to move anywhere. The the values are for carbon (2.4) and hydrogen (2.1), but also
metal is often described as having ‘a sea of electrons’ drifting note how electronegative fluorine is (4.0).
amongst the metal cations. An applied voltage causes the If two butane molecules come together there is little or no
electrons to flow, forming an electrical current. Because no interaction between them. With almost no cohesive forces
energy is used separating electrons from nuclei, the current between molecules, the boiling point of butane is low
obeys Ohm’s law: the current is proportional to the applied (−1 °C). 1-Fluorobutane, by contrast, boils at 32 °C.
voltage.
Table 4.1 Some Pauling electronegativity values
If the conduction band and the valence band do not overlap Element Pauling electronegativity
then a band gap exists. If this is small, the material is a hydrogen, H 2.1
semiconductor. If the gap is large, so that no electrons can carbon, C 2.4
jump up across it, then the material is an insulator. sulfur, S 2.5
chlorine, Cl 3.0
van der Waals forces nitrogen, N 3.0
oxygen, O 3.5
Johannes Diderik van der Waals (1837–1923) was the
fluorine, F 4.0
first Professor of Physics at the Municipal University of
Amsterdam. At a time when some scientists doubted the
very existence of atoms, he published work in which he Dipole–induced dipole interactions
assumed not only the existence of molecules of finite size, If a polarized molecule approaches a neutral molecule at
but also that they attracted one another – though he had first sight it would seem that there would be no interaction.
no idea why. You have only to warm a solid substance like But the electron distribution in a molecule is fluid: even
naphthalene and watch it melt without any decomposition the electrons in a covalent bond are not locked tightly in
to realize that the forces holding the molecules together in place. As a charged molecule (however small the charge)
the solid state must be much weaker than those within the approaches either a neutral molecule or the neutral portion
molecules. Warming is enough to break the intermolecular of another identical molecule, the charge interacts with
40 Unit 1 Module 1 Fundamentals in chemistry

nearby electrons and either attracts them (if positive) or H He

repels them (if positive). The effect is only momentary since Li Be B C N O F Ne

the two particles are in constant motion: but it is enough Na Mg Al Si P S Cl Ar


to form a weak, transient bond. You might expect to find K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
this type of bond both in a mixture of ammonia (which is Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
polar) and liquid butane (which is not).
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac
Induced dipole–induced dipole interaction
These forces, although the weakest of all, are the easiest Figure 4.15 The electronegativity of atoms varies with their
position in the periodic table.
to illustrate. A ‘neutral’ molecule is only neutral when
averaged over a period of time. At any instant the random In summary:
motion of the electrons within it makes the particle, for ■ metals form ionic compounds with non-metals;
that instant, slightly polar. If at that instant the molecule is ■ elements close to each other in the periodic table tend
near to another, it will induce, for that instant, an opposing to form covalent bonds – examples are carbon and
dipole and the two particles will have an attractive force hydrogen forming alkanes and silicon and oxygen
between them. forming silicones.
This is the force responsible for the formation of solid
helium, albeit at a temperature of 0.95 K (−272 °C). The Properties associated with different bond
larger the particle, the more electrons there are to create types
the force and the stronger it is. Table 4.2 gives data for the
melting points of all the noble gases.
Ionic compounds
Table 4.2 The increase in melting point for the noble gases ■ Composed of separate cations (+) and anions (−) in a
correlates with the number of electrons in each atom regular lattice. No separate molecules exist.
Element Atomic number Melting point / K ■ Force is non-directional: ions attract whatever their
He 2 0.95 orientation with respect to each other. The number of
Ne 10 25 neighbours of an ion is determined by the geometry
Ar 18 84 of the structure rather than the atom’s electron
Kr 36 116 structures. An ion can attract any number of ions of
Xe 54 161 opposite charge.
Rn 86 202 ■ High melting point: only the strong ionic bonds are
present and extend in three dimensions.
The periodic table and bond type ■ Substance does not conduct electricity when solid
because ions are immobile, but does conduct when
We can use the periodic table to predict the principle bond molten or in aqueous solution. Ions are then mobile
type between a given pair of atoms. and can move under an applied voltage.
Ionic bonds involve the transfer of electrons from one ■ Soluble in water rather than organic solvents. Ions
atom to the other. This is linked to a large difference in become solvated – form transient bonds to the polar
electronegativity between the two atoms (Figure 4.13). water molecules – which liberates energy sufficient to
Ionic bonds are more likely between elements in Groups separate more ions from the lattice.
I and II and elements towards the top right of the periodic
table – an example is sodium chloride. Less clearly, ionic Covalent compounds
bonds also form between elements at the top right and ■ Composed of separate molecules within which strong
elements in the bottom right of the periodic table – lead covalent (intramolecular) forces hold atoms together.
oxide is an example (see Chapter 15, page 146). ■ Covalent forces are directional, existing between
specific atomic nuclei. Any atom can form a specific
number of bonds.
ITQ 5 Hexane, CH3(CH2)4CH3, has a melting point of −100 °C.
Polythene, CH3(CH2)nCH3, softens just below +100 °C. The value ■ Molecules are held to each another by much weaker
of n in polythene may be several thousand. Suggest a reason for (intermolecular) forces.
the difference in melting points.
Chapter 4 Chemical bonding 41

■ Substances have a low melting point because the Mixed bonds


intermolecular forces are weak.
■ Substances do not decompose at their melting
We have already seen that ionic and covalent bonds are
point because the energy supplied is not enough to the two extremes of a spectrum. We have also seen that
overcome the covalent intramolecular forces. solid covalent materials contain both covalent and van der
Waals forces – iodine, I2, is a good example. The individual
■ Do not conduct electricity when solid, molten or in
molecules are covalently bonded to form the I2 molecules
solution because the structure contains no charged
but the molecules are held together by van der Waals forces
particles.
(Figure 4.16).
■ There may be single, double or triple bonds.
a b

Hydrogen bonds
■ A transient electrostatic attractive force between a
polar molecule and the oppositely charged polar region
of a water-like substance.
shorter larger
■ The positive region is normally a polar hydrogen atom distance, distance,
covalent van der
within a molecule. The negative region is frequently a bond Waals force
polar oxygen atom, but can also involve nitrogen and Figure 4.16 The 3D structure of iodine, showing the covalent
fluorine atoms. bonds between iodine atoms in an iodine molecule and the van
■ Strength is roughly 10% that of the average ionic or der Waals forces between iodine molecules.
covalent bond. Some lattices contain two different bonds within
■ Are sufficient to cause anomalously high melting and themselves. Graphite (an allotrope of carbon) has physical
boiling points for the molecules concerned, which are properties quite different from those of diamond (another
momentarily connected in groups. allotrope of carbon). Although graphite has a similarly high
melting point, it is soft (not hard), it is a good electrical
Metallic bond conductor (not an insulator) and it is a good lubricant (not
■ Produces high electrical and thermal conductivity. an abrasive). These differences can be explained by looking
■ Normally a strong bond. at the structure of graphite (Figure 4.17) and diamond.
■ Metals normally have high density.
Graphite is made up of layers of covalently bonded carbon
atoms, with the layers held together by weaker forces
■ Bond can be visualized as a sea of unattached electrons
produced by wandering electrons (which also give the
washing between positive metal ions. Electrons are free
electrical conductivity).
of their original atoms but act as a ‘glue’ between them.
■ The free electrons are responsible for both electrical
and thermal conductivity.
■ The spherical ions pack together in the most space-
saving way.

van der Waals forces


■ Weak forces between either transient or permanent
dipoles within, or between, molecules.
■ Produce either low or very low melting points and
boiling points (which can be near absolute zero).

covalent
bonds

ITQ 6 Diamond is composed only of carbon atoms (Z = 6). Boron Figure 4.17 The structure of graphite.
nitride, BN, shares many of its properties. Suggest why this may
be so. (B, Z = 5; N, Z = 7)
42 Unit 1 Module 1 Fundamentals in chemistry

Summary
✓ A bond is formed when the attractive forces ✓ Five types of bond are:
between particles outweigh the repulsive forces. ■ ionic
■ covalent
✓ The forces involved in bonding are all
■ hydrogen
electrostatic.
■ metallic
✓ Bond formation normally results in the release of ■ van der Waals
energy.
✓ Each bond type produces characteristic
properties.

Review questions 4 Poly(ethene) (‘polythene’) is a solid. It is made up of


saturated hydrocarbon molecules.
1 A student claimed that ‘ionic, covalent and hydrogen
(a) Which force is responsible for holding the
bonds are all the same, because they all depend on
molecules one to another?
electrostatic attraction’. Explain:
(b) Explain the origin of this force.
(a) why it is true that all three bonds depend on
(c) Explain why water boils at a temperature much
electrostatic attraction;
higher than would be expected from its low
(b) how the properties of substances containing these
relative molecular mass (RMM).
bonds show that the bonds are different from each
other.
Answers to ITQs
2 In single atoms of a metal, such as sodium, the
1 To do so would need the kettle to move spontaneously
electrons are firmly bonded to the atomic nucleus.
from a low energy state to a higher energy state. We
Sodium metal in bulk is a good conductor of
accept as an axiom that this does not happen.
electricity, which means that an electric current can
flow through it. 2 In lithium fluoride the notional charge is the same
(a) What do we mean by ‘an electric current’? as in sodium chloride but the ions are smaller. The
(b) Give a description of a metal structure which electrostatic force between them (which obeys the
makes clear why such a current can flow, and use inverse square law) is therefore stronger.
it to explain why the metal atoms do not fly apart. 3 +
(c) Sodium metal dissolves in liquid ammonia to give H O H
a blue, electrically conducting solution containing
free electrons and solvated sodium ions Na(NH3)x+.
H
How is this ion similar to the sodium ion found in 4 The molecule contains a number (5) of –OH groups
an aqueous solution of sodium chloride, and why? which can form hydrogen bonds with water
molecules, releasing energy to break down the van
3 (a) State two properties of gasoline that make it likely
der Waals forces between the glucose molecules.
that it is:
(i) a mixture 5 The very much longer chain in polythene will be able
(ii) a mixture of covalent molecules. to form many more van der Waals forces thus needing
(b) Contrast the properties of gasoline with the much more energy to separate the molecules, as
properties of molten sodium chloride. Explain compared to the small chain in hexane.
how the bonding in sodium chloride gives rise to 6 There are the same number of bonding electrons
the properties of sodium chloride. between C–C as for B–N and the atoms are of similar
sizes.
43

Chapter 5
Shapes of covalent molecules
Learning objectives
■ Write the Lewis structures for covalent molecules
and ions.
■ Predict the geometrical shape and bond angles
of simple molecules and ions using the VSEPR theory.
■ Outline the basic principles of hybridization.
■ Based on its molecular structure, predict
whether a molecule is polar or non-polar.

Lewis structures Drawing Lewis structures


Gilbert N. Lewis (1875–1946) was an American physical Follow the steps in this list in order to draw the Lewis
chemist who developed the earliest successful model of structure of a molecule.
the chemical bond. According to Lewis’s model, each pair ■ Determine the number of electrons to be included in
of electrons involved in bonding lies in a region of space the structure by counting all the valence electrons for
between two neighbouring atoms. He represented the pair each atom. Valence electrons are the electrons in the
of electrons as a line or a pair of dots. Electron pairs shared outermost orbitals. Add an electron for a negatively
between atoms are referred to as bond pairs. Electrons charged ion and subtract an electron for a positively
present on only one atom are referred to as non-bonding charged ion.
pairs or lone pairs. Covalent bonds can be denoted as
■ Select a central atom. Note that the central atom is
A–B (or A:B), A=B (or A::B) and A≡B (or A:::B), consisting
usually the least electronegative element. Then decide
of one, two and three bonded electron pairs respectively.
which atoms are bonded to which. Place atoms around
Non-bonding electron pairs do not contribute directly to
the central atom using two dots to represent a single
the bonding but they influence the shape and chemical
bond. Hydrogen is never a central atom.
properties of molecules.
■ Complete the octet of electrons on the atoms
Lewis structures account for the formulae of covalent surrounding the central atom, using non-bonding
molecules; they do not indicate the three-dimensional electron pairs (an octet is eight). In the case of
shapes of molecules. hydrogen, there is a maximum of two electrons.
■ After completing the octets, place any remaining
electrons on the central atom as non-bonding electron
pairs.
■ If the central atom has less than eight electrons then
form double bonds or triple bonds by removing one or
two non-bonding pairs of electron from outer atom(s).
Oxygen can form single or double bonds; carbon and
nitrogen can form single, double or triple bonds.
44 Unit 1 Module 1 Fundamentals in chemistry

Worked example 5.1 Worked example 5.2


− Work out the Lewis structure of carbon dioxide, CO2.
Q Draw the Lewis structure for BF4 .
Q
Step 1: Count the valence electrons
A Step 1: First, determine the total number of valence electrons.
A
■ Each boron (B) atom has the electronic configuration one carbon atom 4
1s2 2s2 2p1 and has three valence electrons. The electrons two oxygen atoms (2 × 6) 12
in the inner 1s shell are not included. total 16
■ Each fluorine (F) atom (1s2 2s2 2p5) has seven valence Step 2: The skeletal structure is
electrons, giving a total of (4 × 7) or 28 electrons. O—C—O
■ Since the ion has a single negative charge, add an Step 3: Distribution of the 16 electrons, using two per bond and
additional electron. completing the octet of the outer atoms, gives the following:
■ The total number of valence electrons is therefore equal to
(3 + 28 + 1) = 32 O C O
Step 2: The formula of the ion tells us F
that there are four fluorine atoms bonded Step 4: At the moment the central atom C has only four
to one boron atom. B is the central atom F B F electrons. If a pair of non-bonding electrons is removed from
(the less electronegative) and the fluorine each oxygen atom to form two double bonds between carbon
atoms are placed around it: F and each oxygen then the carbon atom will have eight electrons.

F Step 3: In the next step two dots are O C O


used to represent each bond between
F B F B and F. Now each atom has a full octet of eight electrons.

F You will notice that these structures are very like the
We have used up eight – ‘dot-and-cross’ structures used in Chapter 4, except that in
electrons of the 32 electrons so F a Lewis structure all the electrons are written as dots.
far. Complete the octet of each
of the F atom: F B F Molecular geometry
F The shape of a molecule affects its physical and chemical
properties. For example, the differences in boiling points
This is the Lewis structure for BF4−. Note that the negative of several molecules with similar formulae result from
charge is ascribed to the ion as a whole and not to an individual differences in their structures. In biological reactions, only
atom. molecules of a certain shape and size take part in certain
The electrons forming the – reactions. Small changes in the sizes and structures of
bonds can be shown as lines. F molecules used as drugs may alter their activity, usefulness
and toxicity.
F B F
Molecular geometry refers to the three-dimensional
F arrangement of the atoms or groups of atoms in a compound.

Showing a molecule like this can be very useful because you


Predicting molecular shapes
can see at a glance how many non-bonding pairs there are, This section covers the basis of the valence shell electron
and where they are in the molecule. pair repulsion theory (VSEPR).
The valence shell is the outermost electron-occupied
region of an atom; it contains the electrons that participate
in bonding with other atoms. In a covalent bond, two
ITQ 1 How many lone pairs of electrons are present on (a) Sn in atoms share a pair of electrons, referred to as a bond pair
SnCl2 and (b) Br in BrF2−?
of electrons. In polyatomic atoms where two or more
atoms are bonded to a central atom, electrostatic repulsions
ITQ 2 What would be the Lewis structure of the SO42− ion? among the bonding electron pairs cause them to remain as
Chapter 5 Shapes of covalent molecules 45

far apart as possible. The shape that the molecule assumes, Four electron pairs
as defined by positions of all the atoms, is such that these Four electron pairs round a central atom will lie at the
repulsions are at a minimum. corners of a regular tetrahedron with all the bond angles
In the VSEPR model, double and triple bonds are treated being 109.5°. The central atom is positioned at the centre of
as single bonds. This is an approximation for qualitative the tetrahedron. An example is CH4 and another example
purposes. For accurate predictions of bond angles there is NH4+.
is a difference between single bonds and multiple bonds.
Also, if two or more resonance forms (see page 217) are H H
possible for a molecule, we apply the VSEPR model to 109.5˚

any one of them. For simple molecules, the VSEPR model C C


H H H H
gives excellent agreement between predicted shapes and
the shapes determined from experimental data such as H H
spectroscopic information, bond angle determinations and
X-ray crystallographic data. However, the predictions the
Five electron pairs
model makes about electron density in the molecule are
Five electron pairs round a central atom will lie at the
less reliable.
corner of a trigonal bipyramid. You can imagine the shape
The basic molecular shapes to be made from three atoms at 120° in one plane (as in
the three electron pairs) with an atom above and the final
This first section looks at molecules where the central atom atom below. An example is PCl5.
doesn’t have any lone pairs (non-bonding pairs). All of the
shapes can be modelled by using balloons. Take a balloon,
Cl
Cl Cl
inflate it with air and tie the end. Repeat this with a second
balloon and then tie the two balloons together. Notice the 90˚
Cl Cl
shape they take up. As you continue to add balloons, you P 120˚ P Cl
will be able to observe the corresponding changes in the Cl
geometry. Cl Cl
Cl
Two electron pairs For this geometry, there are two types of positions. You
According to the VSEPR model, a central atom with two have the axial positions, above and below the trigonal
electron pairs only have those two electron pairs in a plane, and the equatorial positions, within the plane. The
straight line. The angle between them will be 180°. An bond angle between an axial atom and an equatorial atom
example is the BeF2 molecule with two electron pairs is 90° and between two equatorial atoms is 120°.
around the central Be atom. The linear arrangement puts
Six electron pairs
the bonding electron pairs as far apart as possible. Other
examples include CO2, HCN and XeF2. Six electron pairs around a central atom will lie at the
180˚ corners of a octahedron. Every bond angle has a value of
90°. An example is SF6.
F Be F
axial
F
Three electron pairs F F
Three electron pairs round a central atom will lie in the S 90˚
same plane at the corners of an equilateral triangle in order
to maximize separation and minimize repulsions. The bond F F
axial equatorial F
angles will all be equal to 120°. An example of a molecule
containing three electron pairs on the central atom is BF3.

F
120˚
B
F F
46 Unit 1 Module 1 Fundamentals in chemistry

Summary ■ In the case of NH3 one position in the tetrahedron will


Table 5.1 summarizes these basic molecular geometries. be occupied by a lone pair of electrons. This pair repels
the bonding pairs more strongly than they repel each
Table 5.1 Basic molecular geometries other. Thus, the molecule has a trigonal pyramidal
Number of geometry.
Molecular geometry Bond angles Examples
electron pairs
2 Linear 180° BeCl2 ■ In the case of OH2, with only three atoms, the

3 Trigonal planar 120° BF3 molecule is planar and V shaped.


4 Tetrahedral 109.5° CH4, NH4+ In CH4, where there are no lone pairs, the bond angles
5 Trigonal bipyramidal 120°, 90° PCl5 are all 109.5°, the normal value observed in regular
6 Octahedral 90° SF6 tetrahedral shapes. For NH3, however, the H–N–H bond
angles are 107.3° due to the presence of the lone pair with
Molecules with lone pairs larger volume requirements forcing the bond pairs closer
together. In the OH2 molecule, where there are two lone
In the examples given so far, the electron pairs around
pairs, the bond angles are even smaller (104.5°).
the central atom are all bonded. However, the shape of
a molecule is governed by the arrangement of both the H
bonding pairs and the lone pairs of electrons. The attractive 109.5˚

forces on the nuclei of two bonded atoms localize the C N O


bonding electron pairs between them. Lone electron pairs
H H H H H 104.5˚ H
on the other hand, are on one atom, are less restricted H 107.3˚
H
tetrahedral trigonal pyramidal V shape
and can occupy a larger region of space. This means that
lone electron pairs will experience greater repulsion from Hydrogen ions in water form the oxonium ion, H3O+. The
neighbouring lone pairs than from bond pairs. These hydrogen ion adds onto one of the lone pairs of the water
strengths of these repulsions fall in the order: molecule without adding any other electrons. The electron
lone pair–lone pair repulsions > lone pair–bond pair structure is then exactly the same as in the NH3 molecule.
repulsions > bond pair–bond pair repulsions The two molecules are said to be ‘isoelectronic’. The
oxonium ion is trigonal pyramidal.
How this affects the shapes of molecules can be shown by
comparing the molecules CH4, NH3 and OH2. The Lewis In general:
structures for these molecules (showing the lone pairs) are ■ molecules with a general formula of AB4, in which
as follows: the central atom (A) is surrounded by four bonded
H electron pairs (B), have a tetrahedral geometry
■ molecules with the general formula AB3E, where A
H C H H N H O is the central atom, B is a bonding electron pair and
H H E a non-bonded pair of electrons, have a trigonal
H H pyramidal shape
■ molecules with the general formula AB2E2 adopt a V
In all three cases, there are four electron pairs on the
shape or angular shape.
central atom. These electron pairs, according to the
VSEPR model, should result in the molecules adopting a
Guidelines for applying the VSEPR model
tetrahedral geometry. However, experiments confirm this
to be true only for CH4. In the case of NH3 three of the four 1 Write the Lewis structure of the molecule.
electron pairs on the central atom are bonded and is one 2 Count the total number of electron pairs (bond pairs
non-bonded. In the case of OH2, two are bonded and two and lone pairs) on the central atom.
non-bonded. The presence of the non-bonded electron 3 Treat double and triple bonds as though they are single
pairs in NH3 and OH2 results in some adjustments to the bonds, i.e. one pair of electrons.
tetrahedral geometry. 4 Predict the overall arrangement of electrons and
geometry of the molecule based on the number of
electron pairs on the central atom.
ITQ 3 Predict the shape of the xenon fluoride molecule XeF2.
(Hint: xenon can hold 10 electrons in its valence shell.)
Chapter 5 Shapes of covalent molecules 47

5 In predicting bond angles remember that: Hybrid orbitals


lone pair–lone pair repulsion > lone pair–bond pair
repulsion > bond pair–bond pair repulsion We saw in Chapter 4 that atomic orbitals can ’co-operate’
with each other to form an equivalent number of hybrid
For organic molecules, when VSEPR is used to describe orbitals. The reason for the change lies in the lower energy
the shape, it is applied to each individual carbon, nitrogen states that are produced. A good example is the isolated
and oxygen atom. Ethane, ethanal, ethene and propanone carbon atom with the electron structure 1s2 2s2 2p2. There
molecules are shown here as examples. are four vacant spaces available if the atom is to have the
tetrahedral
H trigonal planar noble gas structure of neon (1s2 2s2 2p6).
H H When the atom forms bonds with hydrogen, the electron
H C
C C C pairs are furthest apart if they exist at the corners of a
H H O regular tetrahedron. The 2s and the 2p orbitals lose their
H H H H identity and in their place, four equivalent identical orbitals
tetrahedral
are formed. These are called hybrid orbitals and since they
trigonal planar H are formed from one s and three p orbitals, they are called
H O H sp3 hybrids.
H C When two atoms combine, pairs of electrons come under
C H H C C C H the control of both nuclei. The orbitals in which they exist
overlap with each other. Linus Pauling proposed that the
H H H
bonding orbitals of atoms do not just overlap, but combine
Similarly, for molecules with more than one central atom, to form hybrid atomic orbitals. In the compound, these
VSEPR is applied to each central atom. are called molecular orbitals. An s orbital, for example,
can overlap end-on with a p orbital to form an sp hybrid
F H orbital. If the overlap is end-on-end then it is referred to
as a sigma bond (σ). A single bond is made up of one
F B N H sigma bond. There is free rotation about a single bond.

F H

When p orbitals overlap in a side-to-side manner they form


Worked example 5.3
pi bonds (π).
Use the VSEPR theory to predict the shapes of the PF5 molecule.
Q
P has five valence electrons and five F atoms have a total of 35
A valence electrons, giving a total of 40 valence electrons.
The Lewis structure is:
F
F F
B A double bond consists of one sigma bond and one pi bond.
A triple bond consists of one sigma bond and two pi bonds.
F F
Ethane
The central atom, P, has five bonded F
electron pairs so it will have a F In ethane, C2H6, each C atom forms four sp3 hybrid orbitals.
trigonal bipyramidal geometry: Two of these overlap end-on to form a sigma orbital. This
P F
contains two electrons, one from each atom, and constitutes
F a single bond. This is the carbon–carbon single bond. The
F

ITQ 4 On the basis of the VSEPR theory, what would be the ITQ 5 Which of the species in ITQ 4 would have the smallest
shape of the following molecules? bond angles?
(a) ClF3 (b) NHCl3+ (c) XeF4
48 Unit 1 Module 1 Fundamentals in chemistry

remaining three sp3 orbitals form sigma bonds with the Transforming one structure into the other involves only the
s orbital of hydrogen atoms, forming carbon–hydrogen transfer of one electron from one oxygen atom to the other.
single bonds in the two –CH3 groups. In practice, we can imagine that the moving electron takes
up an intermediate position. The two extremes shown in
H H
the diagram are called canonical forms of the structure.
H H The structure exhibits resonance. Experiment shows that
a resonant structure is more stable than would be expected
C C
from either of its canonical forms.
A common structure which relies on resonance for its
H H stability is benzene. For many years after its formula of
C6H6 was determined, chemists could not write a structural
formula for the compound using single, double and triple
Ethene
carbon–carbon bonds. The story is that Friedrich Kekulé, a
In ethene, C2H4, the 2s and 2p orbitals of each carbon German organic chemist (1829–1896), was puzzling on the
combine to produce three sp2 hybrid orbitals that lie in a problem and dreamed one night about a snake gripping its
plane 120° from each other. This leaves one unhybridized own tail. He realized that by writing the structure as a ring
2p orbital. The three sp2 hybrid orbitals form two sigma with alternating double and single bonds, each carbon atom
(σ) bonds with the two hydrogen atoms and one with a could then show its normal valency of four (Figure 5.1).
carbon atom. A pi bond is also formed between the carbon
atoms from the overlap of their unhybridized p orbitals. H H
H
Each carbon atom is bonded to two hydrogen atoms and a H C H H C H H C H
carbon atom, arranged with trigonal planar geometry. C C C C C C

C C C C C C
H C H
Other examples of hybridization H C H H C H
H
Table 5.2 summarizes some geometries that result from the H H

hybridization of other orbitals.


Table 5.2 Molecular geometry and hybridization of orbitals Figure 5.1 The two possible Kekulé structures of benzene.

General formula Electron pairs Hybridization Molecular shape ■ Although this satisfies the demands of valency, it does
AB 1 linear not represent the properties of benzene very well.
AB2 2 sp linear ■ The double bonds should give reactivity: in fact
AB3 3 sp2 trigonal planar benzene is relatively inert.
AB2E 3 sp2 bent, angular, V shaped ■ Double C=C bonds are shorter than single C–C bonds
AB4 4 sp3 tetrahedral yet studies show no such thing in the molecule.
■ Benzene is roughly 150 kJ mol−1 more stable than can
Resonance be predicted from calculation.

In some molecules, electrons can occupy two or more From Figure 5.1, you can see that benzene has two
equivalent positions. One example is the carboxylate ion, canonical forms. This would explain the extra stability.
–COO−. Drawn as structural formulae we can have either But we need to look at the electron distribution to explain
of these two structures: the other problems. Any of the C atoms forms two single
bonds and a double bond. This is the same as in ethene (see
O
O– above). The three single bonds lie in one plane at 120° to
C C each other and the unused p orbital stands at right angles

O O– to the plane so that its lobes overlap on top and beneath it.
The overlapping orbitals merge into hybrids forming one
ring of charge above the plane of the carbon atoms and one
below it (Figure 5.2).

ITQ 6 What is the type of hybridization on the N atom in NO2− ITQ 7 What is the type of hybridization on the C atom in HCN?
and in NO3−?
Chapter 5 Shapes of covalent molecules 49

as CCl4, for example, the geometry is such that individual


bond dipoles cancel each other out. In other cases, the
dipoles do not cancel, resulting in a polar molecule. The
arrangement of non-bonding electron pairs on the central
atom also contributes to the polarity of a molecule since
these contribute to the shape of the molecule.
In order to predict the polarity of a molecule, we must know
Figure 5.2 The hybridization of p orbitals in benzene and the how its polar bonds and non-bonding electrons on the
resulting molecular shape. central atom are arranged. In other words, the molecular
From this we see that there are no separate double bonds. geometry of the molecule must first be determined.
This explains the lack of ethene-like reactivity. The carbon
atoms in the molecule form a symmetrical six-membered Diatomic molecules
ring. Diatomic molecules can be either homonuclear molecules
(A2) or heteronuclear molecules (AB).
Molecular polarity Diatomic molecules consisting of atoms of only one element
In Chapter 4 we saw how bonds between atoms can be (homonuclear), for example H2, Cl2, O2, N2, are linear
polar or non-polar depending on the electronegativities and non-polar. In these molecules the covalent bond is
of the atoms involved. The greater the electronegativity non-polar since the atoms have identical electronegativity.
difference between the atoms, the more polar the bond. Diatomic molecules containing two different atoms, for
A polar bond acts as an electric dipole with a negative (δ−) example CO, HF, NO, are polar. For carbon monoxide, CO,
region or ‘pole’ and a positive (δ+) pole separated by a the measured dipole moment μ = 0.1 D. (The unit used
distance d. The more electronegative atom in the bond has here, the debye, symbol D, is a measure of the electric
the partial negative charge and the bond dipole is directed dipole moment.)
towards this end, shown on a diagram by the arrowhead.
The crossed tail of the arrow is the partial positive pole. Triatomic molecules
– +
Let us consider a linear molecule of general formula AB2, in
A B which A is the central atom and B is more electronegative
d
than A. Each A–B bond is polar, with A having a partial
The dipole moment is a measure of the polarity of a positive (δ+) charge and B having a partial negative charge
molecule. (δ−), The bond dipole is written with the arrowhead
dipole moment = charge × distance between charges pointing towards the negative end, B. Each bond dipole has
μ=q×d a magnitude and a direction. In this linear arrangement, the
dipoles are exactly equal in magnitude but are opposite in
Dipole moments are determined from experiments. A polar
direction. They therefore cancel, resulting in the molecule
molecule has a dipole moment greater than zero and a
being non-polar. The dipole moment is zero. Examples of
non-polar molecule has a dipole moment equal to zero. The
molecules of this type are BeH2 and CO2.
greater the dipole moment, the more polar is the molecule.
– + –

A bond dipole is a vector quantity, which means that it has B A B


a magnitude and a direction. Since a molecule consists of
In the CO2 molecule, the C=O bond is polar. The CO2
one or more bonds, the overall polarity of a molecule will
molecule, however, is non-polar since the dipoles are
be the resultant of the vector combination of the dipole(s)
exactly equal in magnitude but exactly opposite in direction
of its individual bond(s).
(one dipole points to the left and the other to the right).
■ A molecule that consists of only non-polar bonds and – + –
has no non-bonding electrons will be non-polar.
O C O
■ Molecules containing polar bonds can be either polar
or non-polar. ■ The electronegativity values are O = 3.5 and C = 2.5
Molecules containing polar bonds can be non-polar ■ The bond polarity is 3.5 − 2.5 = 1.0.
because of the shape of the molecule. For molecules such ■ The dipole moment is 1.0 + (−1.0) = 0.0
50 Unit 1 Module 1 Fundamentals in chemistry

Trigonal planar geometry


1.57 D 1.87 D
An example of trigonal planar geometry is BF3.
1.01 D
– F

F 120˚ F
+ –
B CH3Cl CH2Cl2 CHCl 3
B F B F F

Guidelines
F – F
F
Here are some guidelines on how to predict the polarity of
simple covalent molecules.
Each B–F bond is polar; the electronegativity difference
1 Based on the electronegativity difference between the
between B and F is 2.0. These three bond dipoles are
atoms in the bonds, determine whether polar or non-
symmetrical and cancel each other out, resulting in the BF3
polar bonds are present.
molecule being non polar (μ = 0).
2 Use the VSEPR theory to predict the shape of the
Tetrahedral geometry molecule.
3 Based the molecular shape of the molecule, determine
NH3 is not trigonal planar because there are three bonded
whether or not the bond dipoles cancel.
atoms and one lone pair of electrons on the central atom.
4 If there are lone pairs on the central atom, determine
NH3 is trigonal pyramidal when you consider the N–H
whether these are arranged so that they cancel.
bonds. However, when you consider the lone pair too, its
overall structure is tetrahedral. 5 If there are no polar bonds or lone pairs present then
the molecule is non-polar.
The nitrogen atom is more electronegative that each
These guidelines are shown in Figure 5.3 as a flow diagram.
hydrogen atom, so the dipoles point toward the nitrogen
and partially reinforce each other. The NH3 molecule is not Are there polar bonds present?

symmetrical: the nitrogen centre is more electron rich and


the dipoles directions do not cancel.
Are the polar
bonds arranged so Are there lone pairs
that they cancel? on the central atom?
N

N
H H
H H
1.47 D
H Molecule
Are these lone pairs
arranged so that
Molecule is
H is polar
they cancel?
non-polar

Tetrahedral molecules with no lone pairs are non-polar


Figure 5.3 Flow chart for determining whether a molecule is polar
since their bond dipoles cancel. Examples include CCl4, or non-polar.
CH4 and SiCl4.
Cl

Two common misconceptions
Cl
We will conclude with two common misconceptions about
C 109.5˚ +
– C –
molecular geometry and polarity.
Cl Cl
Cl Cl
■ Molecules with similar chemical formulae must have
Cl Cl the same geometry. This is not necessarily true. You

cannot predict the shape of a molecule just by looking
Some tetrahedral molecules have more than one type of at its formula. For example, CO2 is linear but SO2 is
atom bonded to the central atom. Molecules of this type angular (V shaped).
are polar since their bond dipoles are not equal and so ■ Molecules that have polar bonds are must be polar.
do not cancel. Good examples of this type of molecular This is also not necessarily true. You need to consider
arrangement are CH3Cl, CH2Cl2 and CHCl3. the geometry of the molecule.
Chapter 5 Shapes of covalent molecules 51

Review questions
Summary
1 Show that the Lewis structures of N2, O2 and NH4+ are
✓ Lewis structures indicate the arrangement of as follows:
electrons in a molecule. +
H
✓ The VSEPR (valence shell electron pair
repulsion) model can be used to predict the N N O O H N H
approximate shape of molecules.
H
✓ VSEPR uses repulsions between electron pairs to
predict the molecular shape. 2 For each of the following molecules and ions, write
✓ Atomic orbitals can reconfigure (hybridize) into the Lewis diagram and then use valence shell electron
different shapes to form lower energy systems. pair repulsion theory (VSEPR) to predict its shape.
(a) XeO3
✓ Two structures resonate if they differ only in the (b) IO4−
arrangement of their electrons. (c) TeCl4
✓ A predicted shape may be modified if resonance (d) BrF3
is possible within the molecule. (e) CH2Cl2
(f) SnCl62−
✓ The shape of a molecule is also affected by the
polarity of bonds within it. 3 NO2+, NO2 and NO2− have O–N–O bond angles
of 180°, 134° and 115°, respectively. Provide an
explanation for this variation in bond angles.
4 Arrange the following molecules and ions in order of
increasing bond angles:
CH3+ NF3 NH4+ XeF4
5 Explain why the PF3 molecule has a dipole moment of
1.03 D but the BF3 molecule has a dipole moment of
0 D.
6 (a) Draw Lewis electron dot representations for the
following molecules and ions:
AlBr4− PCl6− BrF5 NH2Cl2+
(b) Predict the shapes of each of the above molecules
and ions using the VSEPR theory. Draw diagrams,
give names of the shapes and give estimates of
bond angles.
(c) Predict, based on bond dipoles and shapes,
whether each of the above molecules and ions
would have a net dipole moment.
7 Which of the following molecules would you expect
to have a net molecular dipole (polar)? Show your
reasoning.
SiCl4 SiHCl3 SiH2Cl2 SiH3Cl SiH4
8 Discuss in terms of bond polarities, why NaOH is basic
and ClOH is acidic.
52 Unit 1 Module 1 Fundamentals in chemistry

Answers to ITQs Answers to Review questions


1 (a) There are two lone pairs on the Sn atom. 2 (a) XeO3 is trigonal pyramidal
(b) There are three lone pairs on the Br atom. (b) IO4− is tetrahedral
2 (c) TeCl4 is distorted tetrahedral
2–
O (d) BrF3 is T shaped
(e) CHCl2 is tetrahedral
O S O (f) SnCl62− is octahedral

O 3 NO2+ has 16 valence electrons, two bond pairs and no


lone pairs so the ion is linear with O–N–O bond angle
of 180°.
3 A xenon atom has 8 valence electrons: 2 of these
are used forming bond pairs with the fluorine atoms NO2 has 17 valence electrons. Central N atom has a
so 3 lone pairs are left. These repel each other more lone electron and two bond pairs. Shape based on
strongly than they repel the bonding electrons (i.e. the trigonal planar geometry. The single non-bonded
they occupy more space) and so the bonding electrons electron (orbital half filled) takes up less space so the
are forced away from them. The final structure is O–N–O bond opens outward beyond the ideal 120°.
linear. NO2− has 18 valence electrons. Central N atom has a
lone pair of electrons and two bond pairs. Shape based
F Xe F
on the trigonal planar geometry. The non-bonded
electron pair takes up more space so the O–N–O bond
4 (a) ClF3 is T shaped
is pushed inward reducing the bond angle from its
(b) NHCl3+ is tetrahedral
ideal value of 120° to 115°.
(c) XeF4 is square planar
4 XeF4 NF3 NH4+ CH3+
5 ClF3
5 PF3 is trigonal pyramidal and hence is polar. BF3 is
6 sp2 for both
trigonal planar and hence is non-polar.
7 sp
6 AlBr4−, tetrahedral, non-polar
PCl6−, octahedral, non-polar
BrF5, square pyramidal, polar
NH2Cl2+, tetrahedral, polar
7 All the silicon compounds given are tetrahedral.
SiHCl3, SiH2Cl2 and SiH3Cl would be expected to be
polar and SiH4 and SiCl4 would be expected to be
non-polar.
8 Hint: the Na–O bond in NaOH is more polar than the
O–H bond. It is the more polar bond that is likely to
break when the ions form. This means that the OH−
ion is likely to form.
In ClOH the O–H bond is more polar than the Cl–O
bond. This means that the O–H bond is likely to break
when the ions form and so the H+ ion is likely to form.
53

Chapter 6
An introduction to the mole
Learning objectives
■ Define the mole and the term ‘molar mass’.
■ Use relative atomic mass to calculate the relative molecular mass.
■ Write balanced molecular and ionic equations.
■ Interconvert mass, moles and number of particles.
■ Understand the concept of the limiting reagent.
■ Calculate empirical and molecular formulae.
■ Calculate mass and molar concentrations of solutions from theoretical and experimental examples.

Relative atomic mass of elements, Ar


Matter may be described as being made up of entities
which may be atoms, combinations of atoms (molecules) Worked example 6.1
Calculate the Ar of hydrogen, oxygen and magnesium, given
or electrically charged species (ions). The masses of these
entities are infinitesimally small, too small to be measured
Q that their respective actual atomic masses are as follows:
by even the most precise balance. As a result of these small (a) hydrogen = 1.67 × 10−27 kg
masses, scientists have devised a system of measure called (b) oxygen = 2.66 × 10−26 kg
the relative atomic mass scale, in which the mass of an (c) magnesium = 4.00 × 10−26 kg
atom is expressed relative to a standard. The standard used To put an atom’s mass in context, 1 atom of carbon-12 weighs
is the carbon-12 isotope, 126 C, which is assigned a mass of 2.00 × 10−26 kg.
exactly 12.00 atomic mass units (amu).
The relative atomic mass of an element, abbreviated to Ar,
A (a) hydrogen: A r =
1.67 × 10−27
× 12 = 1.002
2.00 × 10−26
is defined as the ratio of the mass of an atom compared to 2.66 × 10−26
1 (b) oxygen: A r = × 12 = 15.96
12 of the mass of an atom of carbon-12. 2.00 × 10−26
Relative atomic mass is given by this formula: 4.00 × 10−26
(c) magnesium: A r = × 12 = 24.00
2.00 × 10−26
mass of 1 atom of the element The values for Ar are very close to the mass numbers for the
Ar =
1 atoms.
12 the mass of 1 atom of carbon-12

This can be re-arranged to give this formula:


Relative formula mass and relative
mass of 1 atom of the element
Ar = ×12 molecular mass of compounds
mass of 1 atom of carbon-12
Compounds can be ionic or covalent (see page 35). Ionic
As Ar is a ratio of two masses with the same units the compounds are made up of formula units while covalent
units cancel out. This means that Ar has no units (it is compounds are made up of molecules.
dimensionless).
The masses of formula units in ionic compounds and of
molecules in covalent compounds are also compared using
the carbon-12 isotope as the standard.
54 Unit 1 Module 1 Fundamentals in chemistry

The relative formula mass is the mass of one formula of these entities. It doesn’t matter if you are talking about
1
unit of the compound compared to 12 of the mass of one atoms, molecules, ions or even electrons. As with Ar and
atom of carbon-12. Mr, the mole is also related to the carbon-12 isotope as a
The relative molecular mass is the mass of one molecule standard. A mole is defined as the amount of substance
1
of the compound compared to 12 of the mass of one atom that contains as many entities as there are atoms in 12 g of
of carbon-12. carbon-12. So, let us now calculate how many atoms there
are in 12 g of carbon-12.
You will find that chemists in real life often refer to formula
units as molecules – this is not precise, but does avoid having 1 atom of carbon-12 weighs 2.00 × 10−26 kg (2.00 × 10−23 g)
to worry about what type of compound you are talking about
when working out its formula mass or molecular mass. As a
therefore 12 g of carbon-12 =
1
(
2.00×10−23
×12 atoms, )
result, the term ‘relative molecular mass’ (abbreviation Mr) which is approximately 6.0 × 1023 atoms of carbon-12.
is commonly used to describe the mass of one formula unit This value of 6.0 × 1023 is the number of entities in one mole
as well as the mass of one molecule. of substance and is referred to as the Avogadro constant.
To determine the Mr of a compound, you need to follow In summary, 1 mole of carbon-12 contains 6.0 × 1023 atoms
these four steps. and has a mass of 12 g.

1 Write the chemical formula of the compound. Avogadro’s constant is the number of particles in 1 mole
of that particle. The value of the Avogadro constant is
2 Identify the atom or atoms present.
6.022 × 1023.
3 Multiply the Ar of each atom by the total number of
each atom present.
4 Add up the numbers obtained in step 3. Worked example 6.3
Use the data from Worked example 6.1 (page 53) to calculate
Values of Ar are often rounded to the nearest whole number. Q the mass of 6.0 × 1023 atoms (in g) for
An exception is chlorine, which is taken as 35.5. For more
(a) hydrogen;
accurate work, values given to 4 significant figures can be
used, as given in the data booklet for the CAPE course. (b) oxygen;
Examples are Cl = 35.45, Fe = 55.85 and Cu = 63.55. (c) magnesium.

(a) hydrogen: 1.67 × 10−24 × 6.0 × 1023 = 1.002 g


A
Worked example 6.2 (b) oxygen: 2.66 × 10−23 × 6.0 × 1023 = 15.96 g
Calculate the Mr of C6H12O6. (c) magnesium: 4.00 × 10−23 × 6.0 × 1023 = 24.00 g
Q
C: 6 × 12 = 72
A Molar mass
H: 12 × 1 = 12
O: 6 × 16 = 96 The mass in grams of 1 mole of a substance is called its
Total = 180 molar mass (M). Molar mass has units of g  mol−1. So,
The relative molecular mass of C6H12O6 is 180. This is often for example, 1 mole of oxygen atoms (O) contains
abbreviated as: Mr [C6H12O6] = 180. 6.0 × 1023 oxygen atoms and has a mass of 16 g. Thus, the
Ar of oxygen is 16 and the molar mass is 16 g mol−1. Note
that relative atomic mass has no units but that molar mass
The mole has units of g mol−1. The mass of 6.0 × 1023 atoms (1 mole)
of an element expressed in grams is numerically equal to
We use special words to mean particular numbers. For the Ar of the element. Although the relative atomic mass of
example: an element and its molar mass are numerically equal, the
pair = 2 decade = 10 (years) dozen = 12 terms should not be used interchangeably.
score = 20 century = 100 gross = 144 Table 6.1 In summary …
mole = 6.0 × 1023 Carbon Oxygen Magnesium
A r = 12 A r = 16 A r = 24
Chemists have defined the mole (symbol ‘mol’) to refer M = 12 g mol−1 M = 16 g mol−1 M = 24 g mol−1
to a specific number of entities, regardless of the nature contains 6.0 ×1023 atoms contains 6.0 ×1023 atoms contains 6.0 ×1023 atoms
Chapter 6 An introduction to the mole 55

Writing chemical equations The physical state of each reactant or product is often given
(in parentheses) next to the formula; these are called state
Here are some examples of everyday reactions: symbols. If we add state symbols to equation 6.2, it becomes:
■ brushing your teeth – sodium fluoride in the HCl(aq) + Na2CO3(aq) → NaCl(aq) + H2O(l) + CO2(g)(6.3)
toothpaste reacts in your mouth to rebuild enamel and
The abbreviations that can be used to indicate the states
control bacteria;
are:
■ cooking on a gas stove – burning chemicals to release
energy; ■ solid = (s)

■ taking antacid tablets – react with the acid in your ■ liquid = (l)
stomach to reduce the acidity; ■ gas = (g)
■ photosynthesis – plants use sunlight energy to produce ■ aqueous solution = (aq); this refers to a substance
sugar. dissolved in water
Chemical reactions take place all around us and even Equation 6.3 is written as a molecular equation in which
inside us! Some reactions are simple, whilst others may the complete neutral formulae for every compound are
be quite complex. During your early studies of chemistry, shown in the reaction.
you would have used a ‘word equation’ to summarize the But look more closely at equation 6.3. For instance, how
chemical reaction between substances. many hydrogen atoms are on each side of the equation?
Chemical reactions can be summarized in words. For There is one hydrogen atom on the left-hand side and two
example, the acid/base reaction in which hydrochloric acid on the right-hand side. Where did this additional hydrogen
reacts with sodium carbonate to produce sodium chloride atom come from? Notice also that there are two sodium
solution, water and carbon dioxide gas can be summarized atoms on the left-hand side and one on the right-hand side.
in a word equation as: Do you think that something needs to be sorted out here?
hydrochloric acid + sodium carbonate → During a chemical reaction, all that changes is the way in
sodium chloride + water + carbon dioxide (6.1) which the atoms are joined together. The total number
of atoms in a chemical reaction remains the same. There
Note the following points:
must be the same number of the same types of atoms on
■ the arrow means ‘produces’ or ‘yields’; both sides of the equation. To ensure that this happens
■ information written above or below the arrow we create a balanced equation, where coefficients are
indicates the reaction conditions; added as needed in front of the formulae of the reactants
■ the substances on the left of the arrow are the reactants; and products. This results in a change in the number of
■ the substances on the right of the arrow are the molecules in the equation.
products. To balance the equation for this acid/base reaction, we put
Although word equations are useful, it is more convenient the coefficient ‘2’ before HCl and NaCl as follows:
to use the chemical symbols of the substances. When 2HCl(aq) + Na2CO3(aq) →
formulae are used, the reaction is represented by a 2NaCl(aq) + H2O(l) + CO2(g) (6.4)
chemical equation, which is a symbolic representation of
what actually happens in a chemical reaction. Check to ensure that the equation is balanced by adding up
the total number of each type of atom on both sides of the
Chemical equations fall into two categories: molecular and equation. If there is no coefficient, a 1 is implied.
ionic. We will first look at molecular equations.
2HCl(aq) + Na2CO3(aq) → 2NaCl(aq) + H2O(l) + CO2(g)
Molecular equations 2 H atoms 2 H atoms
Replacing chemical names in equation 6.1 with formulae 2 Cl atoms 2 Cl atoms
gives: 2 Na atoms 2 C atoms
1 C atom 1 C atom
HCl + Na2CO3 → NaCl + H2O + CO2 (6.2)
3 O atoms 3 O atoms
The equation is balanced since the numbers of each type
ITQ 1 Calculate Mr for the following: of atom on both sides of the equation are equal.
(a) NaCl (b) Cl2 (c) CO2 (d) Al2O3 (e) H2SO4 (f) (NH4)2SO4
56 Unit 1 Module 1 Fundamentals in chemistry

What does the balanced molecular equation 6.4 tell us? Summary
The equation ‘2HCl(aq) + Na2CO3(aq) → 2NaCl(aq) +
Chemical equations may be of three main types, namely
H2O(l) + CO2(g)’ therefore tells us the following:
molecular, complete ionic and net ionic:
■ 2 mol HCl react with 1 mol Na2CO3 to produce 2 mol
■ molecular equations show the complete, neutral
NaCl, 1 mol H2O and 1 mol CO2;
formulae for every compound in the reaction;
■ 73 g HCl react with 106 g Na2CO3 to produce 117 g
■ complete ionic equations show all of the species as
NaCl, 18 g H2O and 44 g CO2.
they are actually present in solution;
■ net ionic equations show only the species that actually
Ionic equations
participate in the reaction.
Reactions occurring in aqueous solution can be written to
show that ionic compounds normally dissociate and form Calculations involving the mole
ions which are free in aqueous solution. For example, the
balanced molecular equation shown above as equation 6.4 When carrying out chemical reactions, what we are able
can be represented by the following expanded equation: to measure is mass and volume of reactants and products.
In order to understand these reactions, and so able to
2H+(aq) + 2Cl−(aq) + 2Na+(aq) + CO32−(aq) →
represent them in chemical equations, we need to be able
2Na+(aq) + 2Cl−(aq) + H2O(l) + CO2(g) (6.5)
to convert these measurements to moles and back again.
In equation 6.5, the reactants and products are shown as they
So far, we have used three ways to express the amount of
are actually present in solution; this is called a complete
substance:
ionic equation. We should notice that in this complete
ionic equation, some of the ions occur unchanged on both ■ mass

sides of the equation. These ions are seen highlighted in ■ moles


red in equation 6.5 and are called spectator ions because ■ number of atoms or particles.
they do not participate in the reaction. They can be omitted Any one of these can be converted to the others, as shown
from the complete ionic equation, leaving us with: in the following worked examples.
2H+(aq) + CO32−(aq) → H2O(l) + CO2(g) (6.6) Do you need a memory aid for the relationship between
Equation 6.6 shows only the species that actually participate moles, mass and molar mass?
in the reaction. An equation such as this is called a net In this triangular arrangement,
ionic equation. the horizontal line in the
It should be noted that when writing complete ionic triangle implies that you need mass
equations, certain substances are written in molecular to divide whilst the vertical
divide
form. Such substances produce few or no ions in solution line implies that you need
and include: to multiply. molar
moles
To find the expression mass
■ metals;
■ solids and precipitates formed upon mixing aqueous for a given term, you
solutions of ionic compounds. e.g. AgCl(s), CaCO3(s); ‘cover up’ that term mulitply

■ non-electrolytes and weak electrolytes such as glucose, (i.e. pretend it’s not
water and ammonia solution; there), and evaluate the remaining terms. For example,
to determine the expression for mass, you cover up ‘mass’
■ gases such as H2(g), N2(g) and CO2(g).
and what you are left with is ‘moles × molar mass’.

ITQ 2 Balance the following equations: Three expressions result from this triangle:
(a) Mg(s) + O2(g) → MgO(s) ■ mass = moles × molar mass
(b) Al(s) + N2(g) → AlN(s)
mass
(c) Al(s) + HCl(aq) → AlCl3(aq) + H2(g) ■ moles =
molar mass
(d) Na(s) + H2O(l) → NaOH(aq) + H2(g)
mass
(e) MnO2(s) + Al(s) → Mn(s) + Al2O3(s) ■ molar mass =
moles
(f) Ca(OH)2(aq) + HCl(aq) → CaCl2(aq) + H2O(l)
(g) CaCO3(s) + H3PO4(aq) → Ca3(PO4)2(aq) + CO2(g) + H2O(l)
Chapter 6 An introduction to the mole 57

Worked example 6.4: converting mass to moles The concept of the limiting reagent
Calculate the number of moles of sodium chloride formula units The mole concept may be likened to the concept of
Q present in 1.17 g of sodium chloride. following a cooking recipe. When making pancakes, for
example, there is a recipe for how the ingredients come
1 What is the conversion required? The quantity given is mass
A and the quantity asked for is moles. together to produce the perfect pancake. In much the same
2 Write a statement of known facts connecting both way, in a balanced equation, there is a ‘recipe’ for how the
quantities. reactants come together to form products. Let us consider
The molar mass of NaCl is 58.5 g mol−1, the following pancake recipe:
i.e. M [NaCl] = 58.5 g mol−1. 3 cups flour + 2 eggs + 1 tbsp baking powder → 12 pancakes
So, 58.5 g of NaCl contains 1 mole of NaCl formula units.
3 Perform the conversion using simple proportions.
+ +
mass of element or compound
number of moles =
molar mass of element or compound
1.17 We can see various relationships between the ingredients
1.17 g NaCl will contain moles
58.5 and the number of pancakes:
= 0.02 moles of NaCl formula units ■ 3 cups flour ≡ 12 pancakes
■ 2 eggs ≡ 12 pancakes
Worked example 6.5: converting moles to mass ■ 1 tbsp baking powder ≡ 12 pancakes

What is the mass of 0.25 moles of H2SO4? These relationships are written as equivalences, where the
Q ‘≡’ sign means ‘is equivalent to’.
You are asked to convert moles to mass. You know that
A M [H2SO4] = 98 g mol−1. 1 mole of H2SO4 weighs 98 g.
In this recipe, there are numerical relationships between
the pancake ingredients and the number of pancakes.
mass = number of moles × molar mass For instance, if you have 3 cups of flour and enough of
So, 0.25 moles of H2SO4 will weigh (98 × 0.25) g = 24.5 g everything else, you can make 12 perfect pancakes.
3 cups flour ≡ 12 pancakes
Worked example 6.6: converting moles to number
This equivalence relationship implies that the ‘flour to
of particles
pancake’ ratio must be 1 : 4 to produce perfect pancakes.
What is the number of sodium atoms in 0.5 moles of the
Q element?
So, how many pancakes can you make if you have 6 cups
of flour and enough of everything else?

A The conversion is from moles to particles: 1 mole of Na If 3 cups flour ≡ 12 pancakes then 6 cups flour ≡ 24 pancakes
contains 6.0 × 1023 Na atoms.
The pancake recipe also provides us with relationships
number of particles = Avogadro’s constant × number of moles
among the ingredients themselves, for example:
So, 0.5 moles of Na will contain 6.0 × 1023 × 0.5
= 3.0 × 1023 Na atoms 3 cups flour ≡ 2 eggs
3 cups flour ≡ 1 tbsp baking powder
Worked example 6.7: converting number of 2 eggs ≡ 1 tbsp baking powder
particles to moles
Calculate the number of moles of magnesium that contains
Q 1.2 × 1024 Mg atoms.
ITQ 3 Balance the following molecular equations (if necessary)
and then write their net ionic equations.
The conversion is from particles to moles. There are (a) HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
A 6.0 × 1023 Mg atoms in 1 mole of Mg. (b) HNO3(aq) + NaOH(aq) → NaNO3(aq) + H2O(l)
number of particles (c) AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
number of moles =
Avogadro’s constant (d) Ba(NO3)2(aq) + H2SO4(aq) → BaSO4(s) + HNO3(aq)
1 (e) HBr(aq) + Ca(OH)2(aq) → CaBr2(aq) + H2O(l)
So, 1.2 × 1024 atoms contains moles × 1.2 × 1024 (f) Pb(NO3)2(aq) + LiCl(aq) → PbCl2(s) + LiNO3(aq)
6.0 × 1023
= 2 moles of Mg (g) AgNO3(aq) + K2CrO4(aq) → Ag2CrO4(s) + KNO3(aq)
58 Unit 1 Module 1 Fundamentals in chemistry

How many eggs are required to go with 6 cups of flour? ■ Calculate the number of moles of each reactant.

If 3 cups flour ≡ 2 eggs then 6 cups flour ≡ 4 eggs ■ Calculate the number of moles of product that should
be obtained from each reactant using the mole ratio
The pancake recipe is much like a balanced equation. For
shown by the balanced equation.
perfect pancakes, all the ingredients must be mixed in strict
■ The reactant that yields the lowest number of moles of
accordance with the recipe. Similarly, when a chemical
product is the limiting reagent.
reaction goes to completion, all the reactants are consumed
Let us now cook our pancakes! Remember that we should
or used up, provided that they are mixed in the mole ratio
get 24 pancakes, but we accidentally burn two and then
as shown by the balanced equation. This ratio is referred to
one fell on the floor! So, we are now left with 21 perfect
as the stoichiometric ratio.
pancakes, which is our actual yield. Our percentage yield
Let us consider the following situation where we set out would be given by the formula:
to make some pancakes by combining all the pancake
actual yield
ingredients that are available in our kitchen. We have 6 percentage yield = ×100
theoretical yield
cups of flour, 8 eggs and 5 tbsp baking powder. How many
perfect pancakes can we make? 21 pancakes
= ×100
24 pancakes
Using the equivalence relationships from our perfect
= 87.5%
pancake recipe:
■ 3 cups flour ≡ 12 pancakes then 6 cups flour ≡ 24
pancakes, so we have enough flour for 24 pancakes Worked example 6.8
■ 2 eggs ≡ 12 pancakes then 8 eggs ≡ 48 pancakes, so we Consider the following equation:
Q
have enough eggs for 48 pancakes Cu2O(s) + C(s) → Cu(s) + CO(g)
■ 1 tsp baking powder ≡ 12 pancakes. Then 5 tbsp baking When 114.5 g of Cu2O are allowed to react with 11.5 g of C,
powder ≡ 60 pancakes, so we have enough baking 87.4 g of Cu are obtained.
powder for 60 pancakes (a) Balance the above equation.
Unless we get more ingredients, we can make only 24 Now determine:
pancakes – this is our theoretical yield. The flour limits (b) the limiting reagent
the number of pancakes we can make. Let us now see (c) the theoretical yield of Cu
which ingredients will be leftover or in excess. (d) the percentage yield of Cu

Flour Eggs Baking powder Cu2O(s) + C(s) → 2Cu(s) + CO(g)


the perfect recipe: 3 cups 2 1 tbsp
A (a) balanced equation
mass / g 114.5 11.5 87.4
we mixed: 6 cups 8 5 tbsp molar mass / g mol −1 143.0 12.0 63.5
based on the flour limitation, the perfect ratio would have number of moles 0.80 0.96 1.38
been: 6 cups 4 2 tbsp theoretical mole ratio 1 1 2 1
excess ingredients: 0 cups 4 3 tbsp (b) 0.80 mol Cu2O should produce 1.60 mol Cu
Since the flour limits the number of pancakes we make, the 0.96 mol C should produce 1.92 mol Cu
flour is called the limiting reagent or the limiting reactant. Cu2O is the limiting reagent since it produces the lower
Observe that the amount of product obtained is controlled number of moles of product (1.60 compared to 1.92).
by the quantity of the limiting reagent available. (c) mass = number of moles × molar mass of Cu
In most chemical reactions, one reactant may be in excess = 1.60 mol × 63.5 g mol−1
whilst the others are used up. The reactant that is used up the theoretical yield of Cu = 101.6 g
in a chemical reaction is called the limiting reagent or actual yield
(d) percentage yield = ×100
the limiting reactant. The limiting reagent is the reactant theoretical yield
that limits the amount of product in a chemical reaction, or 87.4 g
= ×100
in other words, the reactant which produces the smallest 101.6 g
yield of products.
= 86.0%
What is the easiest way to determine the limiting reagent
in a reaction? the percentage yield of Cu = 86.0%
Chapter 6 An introduction to the mole 59

Empirical and molecular formulae


ITQ 4
(a) Given that Ar [Na] = 23.0, calculate the following: The mole concept may also be used to determine the
(i) the mass of 5 moles of Na; formulae of compounds. When describing compounds,
(ii) the number of moles of Na atoms in 57.5 g of the element; several types of formulae can be used. Two such formulae
(iii) the mass of 1.2 × 1025 atoms of Na; are the molecular formula and the empirical formula.
(iv) the number of particles in 34.5 g of the element.
The molecular formula gives the actual number of atoms or
(b) How many molecules of CO2 are present in 880 g of the
ions that are present in one molecule or one formula unit
compound?
of a compound.
(c) What is the mass of 3 × 1021 molecules of HNO3?
The empirical formula gives the simplest whole number
ratio of atoms or ions in a compound.
ITQ 5
(a) A technician allowed 14.4 g of calcium oxide and 13.8 g of The molecular and empirical formulae of a given compound
carbon dioxide to react. This reaction produced 19.4 g of may be the same or they may be different.
CaCO3. The equation is as follows:
■ Instances where they are the same: CO2, for example,
CaO(s) + CO2(g) → CaCO3(s)
has the same molecular and empirical formulae, as do
(i) Which is the limiting reagent? NaCl and H2O.
(ii) What is the theoretical yield of CaCO3? ■ Instances where they are different: the molecular
(iii) What is the percentage yield for the reaction? formula of glucose is C6H12O6, so its empirical formula
(b) Ammonia can be manufactured according to the following is CH2O. In such instances, the molecular formula
general equation: is always a whole-number multiple of the empirical
NO(g) + H2(g) → NH3(g) + H2O(g) formula.
(i) Balance the equation. molecular formula = empirical formula × n,
45.8 g of NO and 12.4 g of H2 are used to produce ammonia. where n = 1, 2, 3, …
(ii) Which is the limiting reagent? Using the example of glucose again, C6H12O6 = CH2O × 6.
(iii) What is the maximum amount of ammonia that can be The subscript of each atom in the empirical formula CH2O
produced?
is multiplied by 6 to obtain the molecular formula C6H12O6.
(c) Ethylene glycol [C2H4(OH)2] can be prepared by the reaction of
ethylene oxide and water, as shown in the following equation: Note that different compounds with different molecular
C2H4O + H2O → C2H4(OH)2
formulae may have the same empirical formula. For
example, the molecules C2H4 and C4H8 have the same
If 200 g of ethylene oxide reacts with 90 g of water and 260
g of ethylene glycol are produced, determine the percentage empirical formula CH2.
yield of ethylene glycol. The empirical formula of a compound can be calculated
(d) Urea (CN2H4O) is prepared by the reaction of ammonia and from either:
carbon dioxide, as shown in the following equation:
■ combustion data, which gives the experimentally
NH3 + CO2 → CN2H4O + H2O
determined masses of the various elements which
(i) Balance the equation.
make up a known mass of the compound, or
125 g of ammonia reacts with 135 g of carbon dioxide.
■ the percentage composition by mass which gives the
(ii) Work out the number of moles of each reactant. percentage by mass of each element in 1 mole of the
(iii) Which is the limiting reagent? compound.
(iv) What is the yield of urea? Once the empirical formula is calculated, the molecular
(e) A student spilled 50 cm3 of 1.0 M hydrochloric acid on the floor formula can then be found provided that the molar mass
in the lab. He attempted to neutralize the acid by adding 50 g
of the compound is known. Worked example 6.9 outlines
of solid Na2CO3 to the spill according to the following reaction:
the procedure for determining the empirical formula and
Na2CO3(s) + HCl(aq) → NaCl(aq) + H2O(l) + CO2(g)
the molecular formula of a compound.
(i) Was the HCl completely neutralized? If not, what mass of
hydrochloric acid was neutralized?
(ii) Did the student add too much or too little Na2CO3? Justify
your answer.
60 Unit 1 Module 1 Fundamentals in chemistry

Worked example 6.9


A 0.450 g sample of an organic acid containing the elements carbon, hydrogen and oxygen was subjected
Q to combustion analysis and the following data were obtained:
■ mass of C = 0.279 g

■ mass of H = 0.0467 g

■ mass of O = 0.124 g

The molar mass of the acid is 116 g mol−1. What are the empirical and molecular formulae of the acid?

Step 1: write down the mass of each element present in the sample of the compound.
A
If percentage compositions by mass are given, assume a 100 g sample and compute the masses of each
element from the given percentages.
C H O
0.279 g 0.0467 g 0.124 g
Step 2: convert each of the masses in Step 1 to moles.
mass
number of moles =
Ar
C H O
0.279 0.0467 0.124
= 0.02325 mol = 0.0467 mol = 0.00775 mol
12 1 16
Step 3: divide throughout by smallest number of moles.
C H O
0.02325 mol 0.0467 mol 0.00775 mol
=3 =6 =1
0.00775 mol 0.00775 mol 0.00775 mol
Therefore, the ratio of C : H : O in the acid is 3 : 6 : 1 and so the empirical formula is C3H6O.
The empirical formula molar mass = (3 × 12) + (6 × 1) + (1 × 16) = 58 g mol−1
We are told that the molar mass of the acid is 116 g mol−1.
The number of empirical formula units in 116 g is given by the formula:
molar mass of compound 116 g mol−1
= =2
empirical formula molar mass 58 g mol−1
There are 2 empirical formula units per mole of acid. The molecular formula is obtained by multiplying the
subscripts of each atom in the empirical formula by this value.
C3H6O × 2 → C6H12O2
The molecular formula of the acid is C6H12O2.

ITQ 6 ITQ 7
(a) The rotten smell of a decaying animal carcass may be attributed to (a) Work out the concentration in mol dm−3 of the
putresine, a compound containing carbon, hydrogen and nitrogen. The following solutions:
results of an elemental analysis of putresine indicate that it contains (i) 25 cm3 of nitric acid which contains
54.50% C, 13.73% H and 31.77% N. Calculate the empirical formula of 2.5 × 10−3 mol HNO3
putresine.
(ii) 500 mL of sodium hydroxide which contains
(b) Nicotine, the main factor responsible for the dependence-forming 1.0 mol NaOH
properties of tobacco smoking, has the following percentage composition (iii) 6.5 dm3 of sodium carbonate which contains
by mass: 74.03% C, 8.70% H and 17.27% N. The molar mass of nicotine 9.5 mol Na2CO3
is 162.23 g mol−1. Calculate the molecular formula of nicotine.
(b) Calculate the number of moles of solute in the
(c) Estradiol is the predominant sex hormone present in females and has a following volumes of solution:
critical impact on reproductive and sexual functioning. Estradiol has the
(i) 25 mL of 0.1 mol dm−3 HCl
elemental composition: 79.37% C, 8.88% H and 11.75% N. Determine
the empirical formula of estradiol. Given that the molar mass of estradiol (ii) 500 cm3 of 0.2 mol dm−3 H2SO4
is 272.37 g mol−1, calculate the molecular formula of estradiol. (iii) 3 dm3 of 0.05 mol dm−3 NaOH
Chapter 6 An introduction to the mole 61

The mole concept applied to solutions Worked example 6.10


The mole concept can be used to measure the strength of Find the concentration in mol dm−3 of:
solutions. In everyday life, we describe the strength of a
Q
(a) a solution containing 3.5 mol H2SO4 in 5.0 dm3 of solution;
solution as dilute, concentrated or saturated. Additionally, (b) a solution containing 0.1 mol H2SO4 in 450 cm3 of solution;
the word ‘concentration’ is often used generally to refer (c) a solution containing 0.020 mol H2SO4 in 25 mL of solution.
to the amount of a particular substance (called the solute)
(a) 5.0 dm3 of solution ≡ 3.5 mol H2SO4
dissolved in another substance (called the solvent). A 3.5
However, there are a couple ways of precisely expressing 1.0 dm3 of solution ≡ 5.0 mol H2SO4 = 0.7 mol H2SO4
the concentration of a solution. The concentration of this H2SO4 solution is
0.7 mol dm−3.
■ Molar concentration or molarity, which gives the
(b) 450 cm3 of solution ≡ 0.1 mol H2SO4
number of moles of solute in 1 dm3 (1000 cm3) of 0.1
1 cm3 of solution ≡ 450 mol H2SO4
solution. The unit of molar concentration can be 0.1
1000 cm3 of solution ≡ 450 ×1000 mol H2SO4
written as mol dm−3, mol/dm3, mol/L or M. This book
≡ 0.22 mol H2SO4
will use mol dm−3 but M is still quite commonly used.
The H2SO4 solution has a concentration of
■ Mass concentration, which gives the mass (in g) of 0.22 mol dm−3.
solute dissolved in 1 dm3 of solution. The unit is (c) 25 mL of solution ≡ 0.020 mol H2SO4
written as g dm−3 or g/dm3. 0.020
1 mL of solution ≡ 25 mol H2SO4
0.020
For molar concentration, we always refer to the volume of 1000 mL of solution ≡ 25 ×1000 H2SO4
the final solution, not to the volume of solvent that may be ≡ 0.8 mol H2SO4
added. The concentration of the solution is 0.8 mol dm−3.
When dealing with the subject of volume as it relates to
concentration, we often encounter a confusion of different Mass concentration
units. Let us try and sort this out …
We have defined mass concentration as the mass of solute
1 dm = 10 cm dissolved in 1 dm3 of solution:
If we cube both sides: mass concentration mass of solute in g
=
in g dm−3 volume of solution in dm3
13 dm3 = 103 cm3
1 dm3 = 1000 cm3 We can rearrange this formula to find the mass of solute
= 1000 mL present in a measured volume of solution once the mass
=1L concentration of the solution is known:
You may come across four different units of volume that mass of solute in g =
are all equivalent: mass concentration in g dm−3 × volume of solution in dm3
1 dm3 = 1000 cm3 = 1000 mL = 1 L
Worked example 6.11
Molar concentration
Find the mass concentration in g dm−3 of:
We have already defined molar concentration as the Q
(a) a solution containing 1.0 g CuSO4 in 50 cm3 of solution;
number of moles of solute dissolved in 1 dm3 of solution: (b) a solution containing 120 g HNO3 in 3 dm3 of solution.
molar conentration number of moles of solute
= (a) 50 cm3 of solution ≡ 1.0 g CuSO4
in mol dm−3 volume of solution in dm3 A 1.0
1 cm3 of solution ≡ 50 g CuSO4
We can rearrange this formula to find the number of moles 1.0
1000 cm3 of solution ≡ 50 × 1000 g CuSO4 ≡ 20 g CuSO4
of solute present in a measured volume of solution once The concentration of this CuSO4 solution is 20 g dm−3.
the concentration of the solution is known:
(b) 3 dm3 of solution ≡ 120 g HNO3
120
number of moles of solute = 1 dm3 of solution ≡ 3 g HNO3 ≡ 40 g HNO3
molar concentration in mol dm−3 × volume of solution in dm3 The HNO3 solution has a concentration of 40 g dm−3.
62 Unit 1 Module 1 Fundamentals in chemistry

The relationship between molar concentration Worked example 6.14


and mass concentration
Determine the molar concentration of a potassium nitrate
Here is a useful memory aid for the relationship between Q solution containing 20.2 g dm−3 of KNO3.
molar concentration, mass concentration and molar mass:
Mr [KNO3] = 39 + 14 + (3 × 16) = 101
A
mass concentration
molar concentration =
molar mass
mass
concentration
20.2 g dm−3
=
101 g mol−1

molar
= 0.2 mol dm−3
molar mass
concentration

Three expressions result from this triangle: Worked example 6.15


350 mL of a sodium chloride solution contains 16.38 g NaCl.
1 mass concentration = Q Calculate the molar concentration of this solution.
molar concentration × molar mass
Firstly, determine the mass concentration of the NaCl solution:
2 molar concentration =
mass concentration A
molar mass 350 mL of solution ≡ 16.38 g NaCl
16.38
mass concentration 1 mL of solution ≡ 350 g NaCl
3 molar mass = 16.38
molar concentration 1000 mL of solution ≡ 350 × 1000 g NaCl = 46.8 g NaCl
The mass concentration of this NaCl solution is 46.8 g dm−3.
We already know that number of moles of substance =
Then we determine the molar concentration of the NaCl
mass of substance (in g)
solution:
molar mass of substance
mass concentration
molar concentration =
If we apply this relationship to solutions, specifically to molar mass
1 dm3 of solution, we can infer that: 46.8 g dm−3
=
number of moles of substance in 1 dm3 = 58.5 g mol−1
mass of substance (in g) in 1 dm3 = 0.8 mol dm−3
molar mass of substance

Worked example 6.16


Worked example 6.12
Given that a solution of potassium manganate(VII) has a mass
Q Calculate the concentration in g dm−3 of a sodium chloride Q concentration of 1.58 g dm−3 and a molar concentration of
solution whose molar concentration is 0.2 mol dm−3. 0.01 mol dm−3, calculate the mass of 1 mol of potassium
(M [NaCl] = 58.5 g mol−1) manganate(VII).
mass concentration = molar concentration × molar mass
A A mass concentration
= 0.2 mol dm−3 × 58.5 g mol−1 molar mass =
molar concentration
= 11.7 g dm−3
1.58 g dm−3
=
0.01 mol dm−3
= 158 g mol−1
Worked example 6.13
What is the mass concentration in g dm−3 of a solution of
Q 0.04 mol dm−3 HNO3?

We first need to calculate the relative molecular mass of HNO3.


A ITQ 8 Work out the concentration in g dm−3 of the following
Mr [HNO3] = 1 + 14 + (3 × 16) = 63 solutions:
mass concentration = molar concentration × molar mass (a) 25 cm3 of sodium chloride solution which contains 20 g NaCl;
= 0.04 mol dm−3 × 63 g mol−1 (b) 50 mL of sodium hydroxide solution which contains 0.04 mol
NaOH;
= 2.52 g dm−3
(c) 5 dm3 of sodium carbonate which contains 0.5 kg Na2CO3.
Chapter 6 An introduction to the mole 63

the unknown solution can be calculated. Worked example


Worked example 6.17
6.18 shows how.
Deduce the value of x in the formula FeSO4·xH2O, given that
Q a solution of FeSO4·xH2O has a mass concentration of During acid/base titrations, you can determine the
30.58 g dm−3 and a molar concentration of 0.11 mol dm−3. concentration of an acid by titrating a known volume of
the acid with a suitable base of known concentration (for
A M [FeSO4·xH2O] =
mass concentration
=
30.58 g dm−3 example sodium hydroxide). Similarly, the concentration of
molar concentration 0.11 mol dm−3 a base may be calculated by titration with a suitable acid of
= 278 g mol−1 known concentration (such as hydrochloric acid or sulfuric
Using the relative molecular mass of 278, we can now deduce acid). An indicator such as methyl orange or phenolphthalein
the value of x in the formula: (Table 6.2) can be used to signal the end-point of this titration
Mr [FeSO4·xH2O] – the point in the titration where the number of moles of H+
= Ar [Fe] + Ar [S] + (4 × Ar [O]) + (x × Mr [H2O]) equals the number of moles of OH−.
= 278 Table 6.2 The colour changes of some common indicators
⇒ 56 + 32 + (4 × 16) + 18x = 278 Methyl orange Phenolphthalein Universal
⇒ 152 + 18x = 278 Colour with acid red colourless red
⇒ 18x = 278 − 152 = 126 Colour with water orange colourless green
126 Colour with base yellow pink purple
⇒x= =7
18 Methyl orange can be ‘screened’ by adding a dye, xylene cyanol, to it. The indicator
The formula is FeSO4·7H2O. is then red in acid, grey about pH7, and green in alkali.

In redox titrations, oxidizing agents react with reducing


Titrimetric (volumetric) analysis agents. The oxidizing agent of choice is often potassium
manganate(VII) (KMnO4), owing to its stability, ease of
So far we have been dealing with theoretical means of storage and the fact that the intense purple colour of its
determining the concentrations of solutions. We have been solution provides its own indication of the end-point of the
carrying out calculations based on the mole concept. The titration.
concentrations of solutions may also be experimentally
In a redox titration to determine the concentration of a
determined in a common laboratory method called a
reducing agent (e.g. Fe2+(aq) or I−(aq)) a solution of
titration. Titration is the process of adding a reactant
purple acidified potassium manganate(VII) of known
a little at a time until the desired result is reached. The
concentration is added from a burette to the reducing
process is sometimes described as a titrimetric analysis and,
agent in a titration flask until the first faint appearance
because volume measurements play a key role in titration,
of a persisting pink colour. This pink colour shows that
it is also known as volumetric analysis. The main aspect
there is a small excess of KMnO4 and hence indicates the
of volumetric analysis involves measuring the volume of
end-point of the titration. Some other oxidizing agents
a solution of accurately known concentration (called the
include potassium dichromate(VI) and iodide thiosulfate (a
standard solution) which then reacts quantitatively with
another solution whose concentration is unknown (called
the analyte). ITQ 9
In a titration, the standard solution is added to a titration (a) A solution of QCl2 has a mass concentration of
flask (usually a conical flask) from a pipette. The solution 0.475 g dm−3 and a molar concentration of 0.005 mol dm−3.
Use this information to determine the relative atomic mass of
of the analyte is then added to the standard solution Q. Then, by using the periodic table, identify element Q.
from a burette until the reaction is complete. The point at
(b) A solution of FeSO4·xH2O was made up by dissolving
which the titration is complete is known as the end-point 55.6 g of solute in 2 dm3 of solution. The molar concentration
or equivalence point. This point occurs when the two of the solution is 0.1 mol dm−3. Determine the value of x in the
solutions just react and neither is in excess. An indicator is formula FeSO4·xH2O.
often added to the contents of the titration flask to detect (c) A solution of hydrated barium chloride, BaCl2·xH2O, has a
the end-point of the titration. The colour of the indicator molar concentration of 0.2 mol dm−3. 40.0 cm3 of this solution
contains 1.952 g of the salt. Calculate:
depends on the acidity of the solution. The volume of
standard solution added from the burette is called the titre. (i) the mass concentration of the solution;
Based on the results of the titration, the concentration of (ii) the value of x in the formula BaCl2·xH2O.
64 Unit 1 Module 1 Fundamentals in chemistry

combination of potassium iodide and sodium thiosulfate).


Worked example 6.18
Hydrogen peroxide can act either as an oxidizing agent or
A standardized solution of sodium carbonate is made by
a reducing agent, depending on the conditions. Q dissolving a 1.49 g sample of sodium carbonate in distilled
water and making up to 250 cm3 of solution. Three
Standard solutions
25.0 cm3 aliquots of this solution are pipetted and titrated
Standard solutions can be prepared in two ways: against a solution of sulfuric acid of unknown concentration
using screened methyl orange as the indicator. The average
■ by dissolving an accurately measured mass of solute in
volume of sulfuric acid used for the titration is found to be
a known volume of solvent; 24.65 cm3.
■ by diluting a more concentrated solution. (a) Calculate the number of moles of sodium carbonate used
Standard solutions should have the following properties: for the titration, if the concentration of the stock solution is
5.62 × 10−2 mol dm−3.
■ high purity – of at least 99.8%; (b) Calculate the accurate concentration of the standardized
■ stability towards air – the composition must not solution of sulfuric acid in mol dm−3.
change when exposed to air and so should not be
(a) The concentration of the standardized solution of sodium
oxidized by air, absorb water vapour, or react with A carbonate = 5.62 × 10−2 mol dm−3
carbon dioxide;
1000 cm3 of solution ≡ 5.62 × 10−2 mol Na2CO3
■ absence of water of crystallization – it should be stable 5.62 × 10−2
1 cm3 of solution ≡ 1000 mol Na2CO3
to drying, i.e. the composition should not alter when
5.62 × 10−2
heated; 25 cm3 of solution ≡ 1000 × 25 mol Na2CO3
■ relatively large formula weight – this minimizes ≡ 1.41 × 10−3 mol Na2CO3
relative errors associated with weighing; (b) This is an acid/base titration, so we need a balanced
■ it should be soluble in common titration media. molecular equation for the reaction:
H2SO4(aq) + Na2CO3(aq) → Na2SO4(aq) + H2O(l) + CO2(g)
The mole concept applied to gases Based on the equation, 1 mol of H2SO4 reacts with 1 mol of
Na2CO3. From part (a), we calculated that 1.41 × 10−3 mol
The amount of a gas is usually measured by its volume. Na2CO3 were used for the titration.
Amadeo Avogadro, an Italian physicist, suggested in 1811
∴1.41 × 10−3 mol Na2CO3 ≡ 1.41 × 10−3 mol H2SO4
that ‘equal volumes of ideal gases at the same temperature
and pressure contain the same number of particles.’ This is 1.41 × 10−3 mol H2SO4 were contained in the average titre
of 24.65 cm3.
now called Avogadro’s law.
Thus, 24.65 cm3 of solution ≡ 1.41 × 10−3 mol H2SO4.
The volume of a gas which contains one mole of gas under 1.41 × 10−3
1 cm3 of solution ≡ 24.65 mol H2SO4
standard conditions of temperature and pressure is called 1.41 × 10−3
1000 cm3 of solution ≡ 24.65 × 1000 mol H2SO4
its molar volume. The molar volume of gas contains the
≡ 0.0572 mol H2SO4
Avogadro number of particles (see page 54). Avogadro’s
number is 6.022 × 1023. The concentration of the sulfuric acid is 0.0572 mol dm−3.

The volume of a mass of gas is influenced by both Through this chapter we have been accumulating ways
temperature and pressure and so the molar volume of a of measuring chemicals. So, in summary, we can say the
gas is usually quoted under one of two sets of conditions. following about 1 mole of nitrogen gas, N2:
■ Standard temperature and pressure (s.t.p.) is a ■ contains 2 mol of nitrogen atoms;
temperature of 273.15 K (0 °C) and a pressure of ■ has a mass of (2 × 14) = 28 g;
101 kPa (1 atm). One mole of a gas at s.t.p. occupies ■ contains 6.0 × 1023 N2 molecules;
22.4 dm3 (22 400 cm3). ■ occupies a volume of 22.4 dm3 at s.t.p.;
■ Room temperature and pressure (r.t.p.) is taken to be a ■ occupies a volume of 24 dm3 at r.t.p.
temperature of 298 K (25 °C) and a pressure of
101 kPa (1 atm). One mole of a gas at r.t.p. occupies
24 dm3 (24 000 cm3).
ITQ 10 20.0 cm3 of a sulfuric acid solution required 22.87 cm3 of
0.158 mol dm−3 KOH for complete neutralization. Calculate the
molar concentration of the H2SO4 in mol dm−3.
Chapter 6 An introduction to the mole 65

Worked example 6.19 Worked example 6.23


What volume is occupied by 8 g of oxygen (O2) at s.t.p.? Calculate the volume of gaseous product formed when
Q Q 1.35 moles of butane undergoes complete combustion at room
temperature and pressure.
1 mol of oxygen has a mass of (2 × 16) = 32 g
A
32 g of oxygen occupy 22.4 dm3 at s.t.p. Avogadro’s law applies only to gases.
22.4
∴ 8 g of oxygen occupy 32 × 8 dm3 at s.t.p. = 5.6 dm3
A
The balanced equation for the complete combustion of butane:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l)
2 mol C4H10 reacts with 13 mol O2 to produce 8 mol CO2.
Worked example 6.20 2 mol C4H10 ≡ 8 mol CO2
8
How many molecules are present in 4.2 dm3 of carbon dioxide 1.35 mol C4H10 ≡ 2 × 1.35 ≡ 5.4 mol CO2
Q at s.t.p.? 1 mol CO2 ≡ 24.0 dm3 at r.t.p.
1 mol of carbon dioxide occupies 22.4 dm3 at s.t.p. and 5.4 mol ≡ 24.0 × 5.4 = 129.6 dm3 CO2
A contains 6.0 × 1023 molecules.
6.0 × 1023
therefore 4.2 dm3 ≡ 22.4 × 4.2 = 1.125 × 1023 molecules
Worked example 6.24
60 cm3 of oxygen is required for the complete combustion
Worked example 6.21
Q of 10 cm3 of a hydrocarbon; 40 cm3 of carbon dioxide is
produced. Determine the formula of the hydrocarbon and hence
Calculate the molar mass of gas X provided that 0.367 g of the
Q gas occupies 200 cm3 at r.t.p.
deduce the balanced equation for the reaction. All volumes are
measured at the same temperature and pressure.
1 mol of gas X occupies 24 000 cm3 at r.t.p. and 200 cm3 of
A gas X weighs 0.367 g. A Let CxHy represent the unknown hydrocarbon.
24 000 10 cm3 of CxHy requires 60 cm3 of O2 to produce 40 cm3 of
24 000 cm3 weighs 0.367 × 200 cm3 ≡ 44 g CO2. Using Avogadro’s law, 10 molecules of CxHy reacts with
The molar mass of gas X is 44 g mol−1. 60 molecules of O2 to produce 40 molecules of CO2. Hence,
1 molecule of CxHy reacts with 6 molecules of O2 to produce
4 molecules of CO2.
Worked example 6.22 CxHy(g) + 6O2(g) → 4CO2(g) + ?H2O(l)
The number of H atoms can be determined indirectly from the
Calculate the volume of oxygen required for the complete
Q combustion of 100 cm3 of propane. Also find the volume of
number of O atoms. There are a total of 12 O atoms on the
left-hand side of the equation and so there should also be 12
carbon dioxide produced. on the right-hand side. The 4CO2 account for 8 such O atoms,
and so that leaves 4 O atoms to be in the H2O. Therefore, there
The balanced equation for the complete combustion of propane:
A must be 4H2O.
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)
CxHy(g) + 6O2(g) → 4CO2(g) + 4H2O(l)
From the balanced equation we can deduce that 1 mol C3H8
For the equation to be balanced, x = 4 and y = 8. The
reacts with 5 mol O2 to produce 3 mol CO2. So, by Avogadro’s
hydrocarbon is C4H8. The balanced equation is:
law, 1 volume of C3H8 reacts with 5 volumes of O2 to produce
3 volumes of CO2. Hence, 100 cm3 of C3H8 will react with C4H8(g) + 6O2(g) → 4CO2(g) + 4H2O(l)
500 cm3 of O2 to produce 300 cm3 of CO2 at the same
temperature and pressure.
66 Unit 1 Module 1 Fundamentals in chemistry

5 200 g of sodium hydroxide is reacted with 300 g of


Summary sulfuric acid.
(a) Write a balanced equation for the reaction
✓ Masses of atoms and molecules are measured occurring.
relative to the mass of an atom of 12C, the mass (b) Calculate the number of moles of each reactant to
of which is taken as 12. 1 d.p.
✓ A mole (mol) of a substance contains 6.022 × 1023 (c) Calculate the limiting reagent.
particles of that substance. This number is called (d) Calculate the mass of salt formed.
the Avogadro constant (L). 6 The following reaction is used to obtain iron from iron
✓ To be valid, chemical equations must contain ore:
the same number of atoms of each individual Fe2O3(s) + CO(g) → Fe(s) + CO2(g)
element on both sides. (a) Balance the equation.
(b) The reaction of 185 g of Fe2O3 with 93.5 g of CO
✓ Ionic equations must show the same total
produces 87.4 g of Fe. Find the percentage yield of
electrical charge on both sides.
iron.
✓ The empirical formula of a compound shows the
7 The titration of a 25.0 cm3 of a H2SO4 solution of
elements present and the simplest ratio between
unknown concentration requires 40.0 cm3 of a
the atoms of each.
0.035 mol dm−3 KOH solution to reach the end-point.
✓ The molecular formula is a simple multiple of Calculate the molar concentration of the H2SO4 in
the empirical formula (the multiplier can be 1). mol dm−3.
✓ The concentration of a solution is quoted in 8 During the complete combustion of an unknown
–3) hydrocarbon, 3.52 g of carbon dioxide and 1.62 g of
moles per litre (mol dm or in grams per litre
(g dm–3). water are collected.
(a) Calculate the mass of:
✓ Indicators are substances which change colour
(i) carbon in 3.52 g of carbon dioxide;
according to the acidity (pH) of their solution.
(ii) hydrogen in 1.62 g of water.
✓ A standard solution is one with an accurately (b) Use your answers obtained in part (a) to calculate
known concentration that is unlikely to change the empirical formula of the hydrocarbon.
with time.
9 A compound X whose molar mass is 46 g mol−1
contains the elements carbon, hydrogen and oxygen.
When 0.544 g of the compound was burnt in oxygen,
Review questions 0.637 g of water and 1.039 g of carbon dioxide
1 What mass of oxygen contains the same number of were produced. Determine both the empirical and
atoms as 48 g of carbon? molecular formula of compound X.

2 What is the percentage by mass of magnesium in 10 Mass spectrometric analysis of a compound Q


magnesium sulfate? reveals a relative molecular mass of 108. Elemental
analysis shows the presence of the elements carbon,
3 How many moles of substance do each of the hydrogen and one other element. When 1.08 g of
following represent? this compound is completely burnt in oxygen, the
(a) 23 g of sodium metal products contain 1340 cm3 of carbon dioxide and
(b) 35.5 g of chlorine gas 448 cm3 of nitrogen dioxide, measured at s.t.p. Find
(c) 132 g of ammonium sulfate the molecular formula of compound Q.
(d) 160 g of iron(III) oxide
4 What volume of a 0.15 mol dm−3 HCl solution is
required to obtain 0.006 moles of the solute?
Chapter 6 An introduction to the mole 67

Answers to ITQs (e) The HCl was completely neutralized


The student spilled 50/1000 mol of HCl. He used
1 (a) Mr [NaCl] = 58.5
50/106 mol of Na2Co3, which is a large excess.
(b) Mr [Cl2] = 71
(c) Mr [CO2] = 44 6 (a) C2H6N
(d) Mr [Al2O3] = 102 (b) empirical formula, C3H6O;
(e) Mr [H2SO4] = 98 molecular formula, C3H6O
(f) Mr [(NH4)2SO4] = 132 (c) C10H14N2

2 (a) 2Mg(s) + O2(g) → 2MgO(s) 7 (a) (i) 0.1 mol dm−3


(b) 2Al(s) + N2(g) → 2AlN(s) (ii) 2.0 mol dm−3
(c) 2Al(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2(g) (iii) 1.5 mol dm−3
(d) 2Na(s) + 2H2O(l) → 2NaOH(aq) + H2(g) (b) (i) 0.0025 mol
(e) 3MnO2(s) + 4Al(s) → 3Mn(s) + 2Al2O3(s) (ii) 0.1 mol
(f) Ca(OH)2(aq) + 2HCl(aq) → CaCl2(aq) + 2H2O(l) (iii) 0.15 mol
(g) 3CaCO3(s) + 2H3PO4(aq) → 8 (a) 800 g dm−3
Ca3(PO4)2(aq) + 3CO2(g) + 3H2O(l) (b) 32 g dm−3
3 (a) HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) (c) 100 g dm−3
H+(aq) + OH−(aq) → H2O(l)
9 (a) magnesium, Mg
(b) HNO3(aq) + NaOH(aq) → NaNO3(aq) + H2O(l)
(b) x = 7
H+(aq) + OH−(aq) → H2O(l)
(c) (i) 48.8 g dm−3
(c) Ba(NO3)2(aq) + H2SO4(aq) →
(ii) 2
BaSO4(s) + 2HNO3(aq)
Ba2+(aq) + SO42−(aq) → BaSO4(s) 10 9.03 × 10−2 mol dm−3 H2SO4
(d) AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
Answers to Review questions
Ag+(aq) + Cl−(aq) → AgCl(s)
(e) 2HBr(aq) + Ca(OH)2(aq) → CaBr2(aq) + 2H2O(l) 1 64 g
H+(aq) + OH−(aq) → H2O(l) 2 20%
(f) Pb(NO3)2(aq) + 2LiCl(aq) → PbCl2(s) + 2LiNO3(aq)
3 (a) 1 mole of sodium metal (Na)
Pb2+(aq) + 2Cl−(aq) → PbCl2(s)
(b) 0.5 mol of chlorine gas (Cl2)
(g) 2AgNO3(aq) + K2CrO4(aq) →
(c) 1 mol of (NH4)2SO4(s)
Ag2CrO4(s) + 2KNO3(aq)
(d) 1 mol of Fe2O3
2Ag (aq) + CrO4 (aq) → Ag2CrO4(s)
+ 2−

4 40 mL
4 (a) (i) 115 g
(ii) 2.5 moles 5 (a) 5.0 mol of NaOH, 3.1 mol H2SO4
(iii) 460 g (b) NaOH is the limiting reagent
(iv) 9 × 1023 particles (c) 355 g
(b) 1.2 × 1025 molecules 6 70%
(c) 0.315 g
7 0.028 mol dm−3
5 (a) (i) CaO
(ii) 26 g 8 C8H18
(iii) 74.6% 9 C2H6O
(b) (i) 2NO(g) + 5H2(g) → 2NH3(g) + 2H2O(g)
10 C6H8N2
(ii) NO
(iii) 26.01 g
(c) 92.2%
(d) (i) 2NH3 + CO2 → CN2H4O + H2O
(ii) 7.35 mol NH3, 3.07 mol CO2
(iii) CO2
(iv) 184.2 g
68

Chapter 7
Gases
Learning objectives
■ Interconvert units of pressure.
■ Outline how the pressure of a gas is determined using a manometer.
■ Use the ideal gas law to calculate pressure, volume, moles of gas or temperature,
given the other three variables.
■ Perform stoichiometric calculations relating the mass of a reactant to the mass,
moles, volume or pressure of a gaseous product.
■ Use the ideal gas law to calculate the molar mass of a gas.
■ Use the kinetic molecular theory of gases to explain each of the gas laws.
■ Explain the difference between real and ideal gases.

Behaviour of gases
Matter exists in three different states: about fixed positions. Liquids have moderate disorder and
■ solids
molecules are relatively free to move. Gases have extreme
disorder and molecules have almost complete freedom of
■ liquids
motion and are randomly arranged.
■ gases.
Gases are homogenous: they mix thoroughly because
In solids – atoms, molecules and ions are held rigidly
their constituent particles are free to move about. Gases
together resulting in a specific shape and volume. Solids
are also compressible: the constituent particles (atoms and
keep their own volume and shape.
molecules) are far apart. Generally the particles occupy less
In liquids – atoms, molecules and ions are held together than 0.1% of the total volume of the container, so when
less strongly than solids. This gives liquids a specific volume pressure is applied they are able to move closer together.
but indefinite shape. They have their own volume but take
the shape of the container. Pressure
In gases – atoms and molecules have little attraction for Gases exert a measurable pressure on the walls of the
each other and are free to move about in any volume or container they occupy. When a gas particle bounces off a
space. As a result, gases have no specific shape or volume. container wall its direction of travel has changed. Therefore
A gas takes both the volume and the shape of its container. a force has acted on it and so the particle has, in its turn,
These states of matter are shown in Figure 7.1. Solids have exerted a force on the container.
an ordered arrangement where the molecules can vibrate
force = mass × acceleration
F = ma
The SI unit of force is the newton (N): 1 N = 1 kg m s−2
Pressure, P, is defined as the force, F, exerted per unit
area, A.
F m×a
P= =
solid liquid gas
A A
The SI unit of pressure is the pascal: 1 Pa = 1 N m−2.
Figure 7.1 A comparison of solids, liquids and gases.
Chapter 7 Gases 69

Atmospheric pressure Boyle’s law: volume and pressure relationship


The mass of the atmosphere, under the influence of Boyle’s law states that the volume of a fixed mass of gas
gravity, exerts a pressure (a force per unit area) on the at constant temperature is inversely proportional to the
Earth’s surface. This is called atmospheric pressure pressure.
and can be quoted in the unit of standard atmospheres.
Atmospheric pressure was originally measured using a What this means is that the product PV is constant
mercury barometer, as shown in Figure 7.2. A pressure when n and T are kept constant. This can be expressed
of one atmosphere (1 atm) supports a mercury column mathematically:
with a height of 760 mm. 1
■ V∝
P
■ PV = k at constant n and T (k is a constant)
■ P1V1 = P2V2

If the volume of a gas is halved, the pressure is doubled


(Figure 7.3).
P = 1.0 atm P = 2.0 atm

760 mm

atmospheric mercury
pressure filled
dish

increase

3
V = 1.0 dm pressure
V = 0.5 dm3

Figure 7.2 A simple mercury barometer.


Figure 7.3 Boyle’s law in practice.
One standard atmosphere (1 atm) = 760 mmHg =
101 325 Pa. Note that ‘standard pressure’ is often quoted a b
as 101 kPa. This is not a convenient figure for simple
calculations and so the ‘bar’ is often used.
P P
1 bar = 100 000 Pa ≈ 1 atm (strictly, 100 000 Pa = 0.986 atm)
The bar and its associated unit the millibar is the unit of
pressure that is often used in weather forecasting. 0 0
V 1
V
The mmHg is also called a torr: 1 mmHg = 1 torr.

c d
Gas laws
The gas laws define the relationships between the four
PV PV
variables that determine the physical properties of any
ideal gas:
■ pressure (P)
0 0
V P
■ temperature (T)
■ volume (V)
Figure 7.4 The pressure/volume relationship for an ideal gas.
(a) The pressure/volume plot shows that P is inversely
■ number of moles (n) proportional to V. (b) A plot of P versus 1/V is linear.
(c, d) A plot of the product of pressure and volume (PV) versus V
or P is constant.
70 Unit 1 Module 1 Fundamentals in chemistry

Charles’ law P = 1.0 atm


P = 1.0 atm

Charles’ law states that the volume of a fixed mass of


gas at constant pressure is directly proportional to its
absolute temperature.

This means that V divided by T is constant when n and P


add
are kept constant. This can be expressed mathematically: V = 44.8 dm3
gas
■ V∝T V = 22.4 dm3
V
■ = k at constant n and P (k is a constant)
T
n = 1 mol n = 2 mol
V1 V2
■ = Figure 7.6 Avogadro’s law in practice.
T1 T2
If the temperature of a gas is doubled, the volume is 1 mole of any gas occupies 22.4 dm3 (more accurately
doubled; if the temperature of the gas is halved, the 22.414 dm3) at 0  °C (273.15 K) and 1.00 atm pressure.
volume is halved. Remember that Charles’ law mentions This volume is called the standard molar volume. There
the absolute temperature, which is measured in kelvin is more about Avogadro’s law in Chapter 6 (page 64).
(K). To get a numerical value for the absolute temperature,
you add 273 (or, more accurately, 273.15) to the Celsius Ideal gas law
temperature. The ideal gas law is a combination of all three of the gas
laws discussed so far. It describes how the volume of a gas is
Volume
affected by changes in pressure, temperature and number
of moles. The ideal gas law assumes that the particles of a
gas have no volume and exert no force on one another –
hence the word ‘ideal’.

The ideal gas law states that PV = nRT, where R is the


gas constant.
Temperature / K
absolute zero
The ideal gas law can be rearranged to show the three gas
Figure 7.5 The volume/temperature relationship for an ideal gas
at constant pressure. The volume/temperature plot shows that V laws:
is directly proportional to T. ■ Boyle’s law: PV = nRT = constant
when n and T are constant
V nR
Avogadro’s law ■ Charles’ law: = = constant
T P
when n and P are constant
Avogadro’s law states that the volume of a gas at a fixed V RT
■ Avogadro’s law: = = constant
pressure and temperature is directly proportional to the n P
when T and P are constant
number of moles of gas present.
A value for the gas constant, R, can be calculated because
This means that V divided by n is constant when T and P 1 mole of an ideal gas occupies 22.4 dm3 at 0 °C (273 K)
are kept constant. This can be expressed mathematically: and 101 kPa (1 atm) pressure.
■ V∝n PV 101 000 Pa × 22.4 × 10−3 m3
R= = = 8.31 J K−1 mol−1
V nT 1 mol × 273
■ = k at constant T and P (k is a constant)
n Note that SI units are used: pressure in Pa, volume in m3
V1 V2 and temperature in K.
■ =
n1 n2
If the number of moles of a gas is doubled, the volume Using the ideal gas law
doubles; if the number of moles of the gas is halved, the Consider the production of hydrogen from the reaction of
volume is halved (Figure 7.6). magnesium with water:
Mg(s) + 2H2O(l) → Mg(OH)2(aq) + H2(g)
Chapter 7 Gases 71

A real gas deviates from an ‘ideal gas’ in two important ways.


Worked example 7.1
For an ideal gas the volume of a gas is mostly empty space,
What volume of H2 is produced at s.t.p. from the reaction of
Q 4.69 g of Mg? and the volume of the molecules themselves is negligible.
In contrast, the molecules in a ‘real’ gas take up part of
A number of moles of Mg =
4.69 g
= 0.193 mol Mg
the total space, which is called the ‘excluded volume’. The
24.31 g mol−1 assumption about an ideal gas is valid at low pressures:
From the equation, 1 mol of Mg produces 1 mol of H2, at 1 atm (0 °C), volume of molecules is 0.05%. However,
therefore, 0.193 mol of Mg produces 0.193 mol of H2. this assumption is not valid at high pressures: at 500 atm
The volume of the gas produced can now be found from the (0 °C), the volume of molecules is 20%.
ideal gas law. It can help in this type of calculation to list all the
For an ideal gas there is no force of attraction between
information you are given and convert the values into SI units:
gas particles or between the particles and the walls of
■ P = 1 atm = 101 000 Pa
the container. This is valid at low pressures because the
■ V = to be found
particles are so far apart. At high pressures particles are
■ n = 0.193 mol
pushed closer to each other and attractive forces become
■ R = 8.31 J K  mol
−1 −1
significant; as a result, the assumption becomes invalid.
■ T = 0 °C = 273 K
Attractions reduce the frequency of collisions with the
PV = nRT walls of the container and therefore a real gas will exert a
nRT 0.193 mol × 8.31 J K−1 mol−1 × 273 K lower pressure.
V= =
P 101 000 Pa
= 4.33 × 10−3 m3 We can show this graphically by finding the values of PV
= 4.33 dm3 for a real gas at various temperatures and pressures. The
gas law PV = nRT implies that the product PV will always be
volume of H2 = 4.33 dm3 at s.t.p.
the same. Taking methane as an example, we get the result
shown in Figure 7.7.
Worked example 7.2 7
ideal
Calculate the molar mass of an unknown hydrocarbon gas with
Q density 1.96 kg m−3 at s.t.p.
6
observed

5
The number of moles of the gas can be calculated using the
A ideal gas law.
200 ˚C

4
■ P = 1 atm = 101 000 Pa
PV / kJ

50 ˚C
■ V=1m
3
3

■ n = to be found –70 ˚C
■ R = 8.31 J K  mol 
−1 −1 2

■ T = 0 °C = 273 K
1

PV = nRT
PV 101 000 Pa × 1 m3 0
n= = = 44.5 mol 0 200 400 600 800 1000
RT 8.31 J K−1 mol−1 × 273 K P / atm

This number of moles corresponds to 1.96 kg of the unknown Figure 7.7 The value of PV at various temperatures and
gas. pressures for methane, a real gas.

1.96 × 1000 g At high pressures, PV is always above the ideal value. This
molar mass = = 44.0 g mol−1
44.5 mol is because the molecules are crammed together, and the
The unknown gas is propane, C3H8. total molecular volume is a significant fraction of the total
volume. PV exhibits a positive deviation from the ideal.
As the temperature falls the molecules approaching the
Behaviour of real gases
walls and about to exert pressure on them are held back
All real gases deviate slightly from the behaviour predicted by the attraction of molecules in the bulk. The lower the
by the ideal gas law because their molecules do interact temperature the more noticeable this effect becomes. PV
with each other and they do have a finite volume. exhibits a negative deviation from the ideal.
72 Unit 1 Module 1 Fundamentals in chemistry

Kinetic-molecular theory
Summary
The kinetic-molecular theory is a century-old model
proposed to help in our understanding of the behaviour of ✓ The state or condition of a gas is described by the
gases. The theory is based on the following assumptions: variables: pressure, volume, temperature and the
quantity of the gas.
■ a gas consists of tiny particles (atoms/molecules) in
constant random motion; ✓ At constant pressure, the volume of an ideal gas
■ the volume of particles is negligible when compared to varies directly with its absolute temperature
the total volume the gas occupies; most of the volume (Charles’ law).
of a gas is empty space;
✓ At constant temperature, the pressure of an ideal
■ gas particles act independently of each other; there are
gas varies inversely with its absolute volume
no attractive or repulsive forces between particles;
(Boyle’s law).
■ collisions of gas particles with themselves or the walls
of the container are elastic, i.e. the total kinetic energy ✓ The kinetic-molecular theory accounts for the
of the particles is constant at constant T; properties of an ideal gas by making the following
■ the average kinetic energy of the gas particles is assumptions about the nature of the gas:
proportional to the absolute temperature of the sample. ■ the molecules are in constant, random motion
■ the volume of the gas molecules is negligible in
Kinetic-molecular theory can be used to explain the
relation to the volume of its container
individual gas laws.
■ there are no attractive forces among the gas
Boyle’s law (V ∝ 1/P) molecules
■ the average kinetic energy of the gas molecules
The gas pressure measures the number and forcefulness
of the collisions between gas particles and the walls of the is proportional to the absolute temperature.
container. Therefore the smaller the volume (at constant T ✓ The ideal gas equation PV = nRT, where T is in
and n), the closer together the particles are and the greater kelvin, is the equation of state for an ideal gas.
the number of collisions. Most simple gases obey the ideal gas equation
P ↑ at pressures of about 1 atm and temperatures of
V ↓ 300 K and above.
Charles’ law (V ∝ T) ✓ Departure from ideal gas behaviour increases as
Temperature measures the average kinetic energy of gas the pressure increases and as the temperature
particles. The higher the temperature (at constant n and P), decreases.
the faster the movement of the particles and the more space
✓ The ideal gas equation is useful for calculating P,
required to avoid an increase in the number of collisions
V, T and n (number of moles).
with the walls of the container.
T ↑ ✓ Real gases depart from ideal behaviour because
V ↑ their molecules have a finite volume and

∝ n)
experience attractive forces for one another on
Avogadro’s law (V collision.
The more particles in a gas (at constant T and P), the more
volume the particles need to avoid increasing the number
of collisions with the walls of the container.
n ↑
V ↑

Dalton’s law (Ptotal = P1 + P2 + P3 + …)


The chemical identity of the particles is irrelevant. The
pressure of a fixed volume of gas is dependent on T and n.
The pressure exerted by a specific kind of particle depends
on the mole fraction of that kind of particle in the gas
mixture. In a mixture the gases do not act on each other.
Chapter 7 Gases 73

Review questions Answers to Review questions


1 A student collected natural gas from a laboratory gas 1 16.0 g mol−1, gas is methane
jet at 25 °C in a 500 cm3 flask until the pressure of the 2 2.42 × 1022 gas molecules
gas was 0.722 atm. The gas sample weighed 0.236 g at
25 °C. Calculate the molar mass of the gas. 3 (a) 720 Torr; (b) 95992 Pa

2 A deep breath of air has a volume of 1.05 dm3 at a 4 200 K


pressure of 740 mmHg. Considering that the body’s 5 509 K
temperature is 37 °C, calculate the number of
6 24.4 g
molecules in the breath. (1 atm = 760 mmHg.)
7 1.68 × 103 g N2
3 A cylinder is filled with 70.0 g propane gas (C3H8) at
a pressure of 840 Torr. What would be the pressure of 8 Less than 100 °C since atmospheric pressure will be
the cylinder in (a) Torr and (b) Pa if 10.0 g of propane less at the higher altitude.
gas is removed at constant temperature? 9 (a) In the refrigerator, air is cooled so volume
(1 Torr = 133.3 Pa; 760 Torr = 1 atm) decreases.
4 The pressure of a sample of gas with an initial pressure (b) Removing from the refrigerator, air is heated so it
of 3.50 atm and a temperature of 100 K is to be will expand.
increased to twice its original value at a constant 10 The increase in pressure in the pressure cooker allows
volume. To what temperature must the gas be food to be cooked at temperatures greater than 100 °C
brought? without the water boiling away, thus reducing the
5 An engineer designed a new piston-cylinder device cooking time.
and pumps air in at 25 °C. The volume at this
temperature is 70.2 cm3. At what temperature (in
kelvin) will the volume be 120.0 cm3?
6 Sodium, a Group I metal, reacts vigorously with
chlorine gas to produce sodium chloride. Calculate the
mass of sodium chloride that will be produced when
5.25 dm3 of chlorine gas at 0.95 atm reacts with 17 g
of sodium at 293 K. (Hint: consider which reactant is
limiting.)
7 A tank is filled with 600 dm3 of nitrogen gas at
20 °C. After sometime it is discovered that the tank
has developed a leak. The tank is resealed. If the
pressure of the tank after sealing it is 2.40 atm,
determine the mass of nitrogen that remains in the
tank.
8 The Blue Mountain peak in Jamaica is 7402 ft above
sea level. Would you expect the boiling point of water
at the peak to be greater or less than 100 °C? Explain
your answer.
9 Use the kinetic-molecular theory to predict what
would happen if a balloon is filled with air, tied and
(a) placed in a refrigerator and then (b) removed from
the refrigerator.
10 Use the kinetic-molecular theory to explain how a
pressure cooker works.
74

Chapter 8
Thermochemistry
Learning objectives
■ Explain the concept of temperature.
■ Distinguish heat and heat capacity.
■ Explain what is meant by heat and work.
■ Distinguish between heat and work.
■ State the first law of thermodynamics; conservation of energy.
■ Define state functions.
■ Describe how to measure heat with a calorimeter.
■ Contrast enthalpy and internal energy.
■ Define enthalpies of reaction.
■ Define standard state enthalpies of reaction.
■ State and use Hess’s law.
■ Illustrate, using energy profile diagrams, the concepts of exothermic
and endothermic reactions.

Introduction to thermodynamics
Thermodynamics is the branch of science that describes Energy is defined as the capacity to do work.
the relationship between heat, work and other forms of In chemistry we commonly speak of ‘heat’. Heat is the
energy. It allows us to predict whether or not a physical energy that flows to a region of low temperature from a
or chemical change is possible, but gives no information region of higher temperature.
about the rate at which changes can take place. Rates of
reaction are studied in Chapter 9. Units of heat, work and energy
The prefix thermo originates from the Greek word that The unit of work is the joule. This unit is named in
means heat and dynamics comes from the word for force. recognition of the work done by James Joule (1818–1889),
By combining these two meanings, we could say that a British physicist and brewer, who carried out much work
thermodynamics focuses on the force of heat or other forms in the field of thermodynamics. 1 joule is the work done
of energy. Thermochemistry is a branch of thermodynamics when a force of 1 newton (kg m s−1) is used to move an
that focuses on the study of energy changes that take place object by 1 metre in the direction of the force.
during physical and chemical processes. Our focus in this
1 J = 1 N m
chapter is on thermochemistry.
Joule discovered that work can be converted to heat and
Thermochemistry describes the absorption or release of
vice versa, so the joule is used to measure energy in the
energy associated with a chemical reaction.
form of both heat and work. Energy is measured in units
Changes in energy content accompany all physical and of joules (J) or kilojoules (kJ). Older units, still used for the
chemical processes. Unlike matter, which can be seen and energy content of food, include calories (cal) or kilocalories
touched, one cannot see or touch energy. Like matter, (kcal).
energy can neither be created nor destroyed but energy
1 cal = 4.184 J
can be changed from one form to another. Note that matter
and energy can be interconverted in nuclear reactions (see 1 kcal = 4.184 kJ = 1 Cal; this is the ‘calorie’ used in food
Chapter 3). data
Chapter 8 Thermochemistry 75

Energy change in a reaction and serves as a measure of it. At low temperatures, the
average kinetic energy of the particles is lower than that
Matter always exists with energy that enables it to do
at higher temperatures; molecular motion is less at the
work. For example, some of the energy in oil is liberated
lower temperatures. An increase in temperature indicates
(as heat) during combustion. This heat energy can be used
an increase in kinetic energy. Atoms and molecules at
to make machines do work. The net energy change of a
low temperatures (slower moving particles) are perceived
reaction is the energy difference between the reactants and
as being ‘cold’ while those at high temperatures (faster
the products.
moving particles) are perceived as being ‘hot’.
ΔE = Eproducts − Ereactants
Temperature is an intensive property, that is, it is not
where Δ means ‘the change in’ dependent on the size of the sample. For example, if we
have a container with 50 cm3 of water at 30  °C and we
Stored energy combine it with 30 cm3 of water from another container
Different forms of stored energy fall into two main at the same temperature, the temperature of the 80 cm3 of
categories: water is still 30 °C even though the volume has increased.
Quantities that are dependent on size for example, mass
■ kinetic energy, which is due to the motion of the
and volume, are extensive properties.
particles;
■ potential energy, which is stored in bonds and is also When two bodies at different temperatures come in
related to the position of the object. contact with each other heat will flow from the hotter to
the cooler until they reach the same temperature called the
In chemistry, potential energy results from attractions
thermal equilibrium temperature. The zeroth law of
and repulsions between charges; for example protons and
thermodynamics states that:
electrons in an atom. The magnitude of this energy differs
with the distance between the charges. Potential energy If two bodies are in thermal equilibrium with a third body
changes therefore take place during the transfer of electrons then they are in thermal equilibrium with each other.
or the sharing of electrons when bonds are formed between
atoms, or the smaller interactions making up van der Waals Heat and heat capacity
bonds. It is sometimes called chemical energy. Some of this
energy is released when substances react to form something Don’t confuse the concept of heat with that of temperature.
more stable. The study of thermochemistry tells us how If you have swum for too long and you feel cold, would
energy changes are observed, measured and predicted for you rather lie in a bath that is full of warm water or have
chemical and physical processes. Definitions of the terms someone hold a lighted match under you? The water in
heat, temperature, energy and work are central to the the warm bath has lots of heat but does not have a high
understanding of this topic. temperature. The lighted match doesn’t have much heat
but does have a high temperature.
Temperature Heat causes the temperature of an object to change. When
Atoms and molecules are in constant motion. Even an object absorbs heat, its temperature may increase, or it
bodies that appear stationary to the naked eye contain may melt or boil. When it loses heat to its surroundings its
atoms moving with random motion. Not all particles in temperature may decrease or it may condense or freeze.
an object will move at the same speed; some have lower The amount of heat needed to raise the temperature of
kinetic (movement) energy and so move more slowly 100 cm3 of water by 1 °C is not the same as the heat needed
than others. The average kinetic energy of all the particles to do the same to 100 cm3 of other liquids.
in an object is proportional to the absolute temperature The heat capacity, C, of an object is the quantity of heat
(in kelvin) of the object. The temperature of an object is required to raise its temperature by 1 kelvin.
therefore determined by the kinetic energy of its particles heat exchanged
heat capacity =
temperature change
ITQ 1 What kind of energy change do you associate with each of ΔH
C= where ΔT = Tfinal − Tinitial
the following? ΔT
(a) car battery; The quantity of heat exchanged (q) is given by:
(b) steam engine;
q = C × ΔT
(c) furnace.
76 Unit 1 Module 1 Fundamentals in chemistry

ΔT can have a negative or positive value. It will have the Table 8.1 Specific heat capacities of some common substances
same numerical value whether it is in degrees Celsius or Substance Specific heat capacity / J g−1 K−1
kelvin. For example, if the final temperature is 50 °C and H2O(l) 4.1840
the initial temperature is 40 °C, then NH3(l) 4.70

ΔT = 50 °C − 40 °C = 10 °C Fe(s) 0.449


Al(s) 0.901
or, in kelvin,
Cu(s) 0.38
ΔT = 323.15 K − 313.15 K = 10 K stainless steel 0.51

Regardless of the units, the temperature changes by 10 ethanol 2.42

units. N2(g) 1.040


NaCl(s) 0.8641
The value of the heat capacity varies with the size or
amount of substance (it is an extensive property). Larger
amounts of a substance will have a greater heat capacity Worked example 8.1
than smaller amounts of the same substance. Heat capacity
The specific heat capacity of iron is 0.449 J g−1 K−1. Calculate
is more usefully described in terms of an intensive property Q the heat capacity in J °C−1 of 3.00 g of iron.
– specific heat capacity or molar heat capacity.
heat capacity = specific heat × mass
The specific heat capacity (specific heat) c, is the amount of A
= 0.449 J g−1 K−1 × 3.00 g
heat necessary to raise the temperature of 1 g of a substance
= 1.347 J K−1 = 1.347 J °C−1
by 1 °C (or 1 K). The SI units of c are J g−1 K−1.
C
c=
mass Latent heat
The equation for heat change then becomes:
Heating a substance does not always make it get hotter.
q = c × m × ΔT While at first sight that seems like an odd statement,
The greater the mass of a substance the more heat is consider what happens when we heat pure water at 1 atm
required to raise its temperature. pressure. The temperature increases until the water boils
at 100  °C. The water then remains at this temperature,
By convention, if heat is absorbed into a system, the heat
even with added heat, until it all completely evaporates
change (Δq) is positive. If heat is lost from a system to the
(changes to the gas phase).
surroundings, Δq is negative.
Heat is entering the system without being detectable as
We may express heat change in terms of the molar heat
a change in temperature. The heat entering the system
capacity, which is the heat required to raise the temperature
provides the energy required to overcome the attractive
of one mole of a pure substance by 1 K (1 °C):
forces between the particles in the liquid to enable the
C particles to become a gas.
cm =
number of moles
This kind of heat is called latent heat (‘latent’ in this
q = cm × number of moles × ΔT
context means ‘hidden’). Latent heat is involved when
The equations given above involving specific heat there is a change in the phase (state) of the substance.
are used only when there is a change in temperature The changes of state are when a substance changes from
without any phase change or chemical reaction. For solid to liquid (melts), liquid to solid, (freezes), boils (liquid
example, when ice at 0 °C absorbs heat it melts to form to vapour) or condenses (vapour to liquid). These are all
liquid water at 0 °C. In this case ΔT is equal to zero but q shown on Figure 8.1.
for the process is not zero.

Table 8.1 lists the specific heat capacities of some common


substances. Note that water has a very large value, second
ITQ 3 The specific heat capacities of aluminium and water are
only to liquid ammonia.
0.902 J g−1 °C−1 and 4.184 J g−1 °C−1 respectively. Equal masses
of water and aluminium were heated with 1 kJ of electrical energy
ITQ 2 Suggest an important consequence of the large value of at room temperature. Which of the two substances (water or
the specific heat capacity of water. aluminium) would you expect to get hotter? Explain why.
Chapter 8 Thermochemistry 77

6 E = E final – E initial
latent heat gas
liquid / gas surroundings
(vaporization)
Energy out of system
condensation to surroundings: – sign
vaporization
liquid
T / ˚C

freezing system
Energy into system from
melting surroundings: + sign

solid / liquid Figure 8.3 The movement of energy between a system and its
latent heat
solid (fusion) surroundings.

Heat added
Heat and work
Figure 8.1 Latent heat of fusion and vaporization.
When a force moves an object, work is done. The quantity
Heat and the kinetic-molecular theory of work done is defined as the force multiplied by the
distance moved in the direction of the force:
Thermodynamics divides the universe into a ‘system’ and
its ‘surroundings’ (Figure 8.2). The system is the small part work = force × distance = F × d
that we are interested in investigating. For example, it could The unit of work is the newton-metre, usually called the
be the reaction mixture in a beaker. The surroundings joule (J).
are everything else outside the system, i.e. the rest of
Chemical reactions can do work electrical work by forcing
the universe. A boundary separates the system and its
an electric current through a wire, e.g. an electric current
surroundings. This boundary can be real or imaginary, rigid
through the filament in a light bulb. In other cases, chemical
or elastic. For example, it could be the glass of the beaker
reactions can do work of expansion because of the changes
or a cylinder wall. The boundary can be an ideal conductor
in volume of the system during the reaction.
of heat or an insulator.
In order to better understand how work of expansion is
surroundings
done by a chemical reaction, consider the combustion of
ethane gas with oxygen occurring in a cylinder with a
piston (a closed system), as shown in Figure 8.4.
system
P= F
A
P= F
A
system boundary

Figure 8.2 The surroundings and the system – that’s all there is,
according to thermodynamics.
d
A system can be described further as open, closed or
reaction
isolated.
w =Fxd
■ In an open system both matter and energy are =–PxAxd
= – P6V
exchanged with the surroundings. Some examples
include an open reaction flask, the human body and before reaction after reaction
(initial state) (final state)
the engine of an car.
Figure 8.4 Calculating work done during expansion.
■ A sealed flask would be a closed system since it has a
fixed amount of matter but is able to exchange energy 2C2H6(g) + 7O2(g) → 6H2O(g) + 4CO2(g)
with the surroundings.
Before the start of the reaction, the pressure of the gases
■ An isolated system is sealed and insulated from the pushing up on the piston is balanced by the weight of the
surroundings and can exchange neither matter nor
energy with the surroundings. A sealed vacuum flask
ITQ 4 In cold climates, blossom on fruit trees is sometimes spoilt
is an example of an isolated system. by sub-zero temperatures before dawn. The farmer may spray
his trees with water, which freezes on the branches. Suggest how
this helps to preserve the blossom.
78 Unit 1 Module 1 Fundamentals in chemistry

piston and so the total volume of the gases is constant. can lose or gain energy but any changes in the energy of
9 moles of reactants (2 mol ethane plus 7 mol of oxygen) the system must be accompanied by an equivalent change
react to produce 10 moles of products. The volume of gas in the energy of the surroundings so as to ensure that the
after the reaction is therefore greater than the volume total energy of the universe is constant.
before the reaction. If the reaction takes place in a sealed ΔEsystem + ΔEsurroundings = 0
container at constant pressure and temperature, with a
movable piston, then the increase in the volume of the gas In thermodynamics, the energy of a system is referred to
would push the piston outward against the force of gravity. as internal energy, U. Internal energy is proportional
Work is therefore done by the system (and in opposition to to the sum of the system’s kinetic energy (energy due to
atmospheric pressure, thus −Pext) and is given by motion of atoms, molecules, etc.) and the potential energy
(energy due to the position or ‘stored’ energy in the case of
w=F×d (8.1) chemical reactions involving bonds).
where d is the distance moved by the piston.
The internal energy of an ideal gas at temperature T has
The pressure exerted by the gas on the piston (Pext) is equal
zero potential energy so its internal energy is the kinetic
to the force (F) with which it pushes against the piston
energy at T which is given by the following equation:
divided by the surface area (A) of the piston:
3RT
F U=
Pext = or F = Pext × A 2
A
where R is the universal gas constant (see Chapter 7) and
If this expression for F is substituted in equation 8.1, the
T is in kelvin.
work done is
For non-ideal and more complex systems, the internal
w = (P × A) × d = P × (A × d)
energy cannot be determined directly. However, changes
The product A × d is equal to the change in volume ΔV in the internal energy (ΔU) can be determined from
when the gas expands. Therefore: temperature changes of the system and are defined as
w = Pext ΔV the difference between the initial and final values of the
internal energy.
In an expansion (an increase in volume) ΔV is positive,
work is done by the system, so the system loses energy and ΔU = Ufinal − Uinitial
w = −Pext ΔV is negative. Since the internal energy is proportional to its temperature,
In a contraction (a decrease in volume) ΔV is negative, an increase in temperature results in an increase in internal
work is done by the surroundings on the system so the energy and ΔU will be positive.
system gains energy and w = −Pext ΔV is positive.
Inter-conversion of heat and work
If there is no change in volume, then no work is done.
According to the first law of thermodynamics, for a
closed system, energy transfer between the system and
The first law of thermodynamics
its surroundings can only be in the form of heat or work.
Energy conservation The change in the internal energy is therefore a balance
between the heat (q) and the work (w) that cross the
The first law of thermodynamics is the result of the
boundary between the system and its surroundings.
observations of the British physicist William Thomson (later
Lord Kelvin) and the German physicist Rudolf Clausius. ΔU = q + w
Working independently, they observed that whilst neither This equation also shows that the amount of heat generated
heat nor work is conserved in nature, energy is conserved. by a system can be limitless as long as enough work is done
The first law of thermodynamics states that energy is on it to compensate for its loss of internal energy. Similarly,
conserved in a closed system. Energy is neither created the amount of work done by a system can be boundless if
nor is it destroyed. It is converted from one form to enough heat is pumped into it to compensate for the load
another. on its internal energy. If either heat or work is removed
from the system without any compensation, then the
The first law of thermodynamics can be restated as: ‘the internal energy of the system will decrease until the system
total energy of an isolated system is constant’. A system can longer generate heat or do work.
Chapter 8 Thermochemistry 79

Worked example 8.2 State functions


A state function is property of a system whose value
A gas absorbs 600 J of heat energy and is compressed from
Q 50 dm3 to 40 dm3 by an opposing pressure of 4.0 atm. depends only on the state of the system and not on the
Calculate the change in the internal energy (ΔU ) for this path used to arrive to that state.
process.
Temperature, for example, is a state function because the
ΔU = q + w net change in temperature of a system, ΔT, depends only
A on the initial and final values regardless of how many
q = +600 J (heat absorbed by the system)
4 atm = 4 × 101 000 Pa times the system may have been heated or cooled. ΔT =
40 50 Tfinal − Tinitial. Internal energy is also a state function since it
40 dm3 = m3 = 0.04 m3; 50 dm3 = m3 = 0.05 m3 is proportional to temperature.
1000 1000
w = −PΔV = Popposing × (Vfinal − Vinitial ) State functions are reversible; that is, they can return to
= −4.0 × 101 000 Pa × (0.04 m3 − 0.05 m3) their initial condition. The overall change in a state function
= 4040 J (work done on the system is positive) is zero when the system returns to its original condition.
ΔU = q + w = 600 J + 4040 J = 4640 J
The internal energy of the system increases by 4640 J due to Conventions
absorption of 300 J of heat and 4040 J of work energy. In equations, state functions are represented using upper
case symbols, such as T, P, V and U. Properties that are not
We can now explain the concept of latent heat using the state functions are represented using lower case symbols,
first law of thermodynamics. When heat is applied to a such as w, q, m and n.
system it can increase the temperature (ΔU is positive) or
it can do work. Whereas the increase in temperature can
Calorimetry
be detected, work on the system (ΔU = 0) cannot and it is
therefore ‘latent’. The amount of heat absorbed or given off during a chemical
reaction can be measured using a calorimeter. A calorimeter
There is a convention that we follow:
is an insulated container with a thermometer.
■ ΔU is negative when the system loses energy to its
surroundings (Ufinal < Uinitial) or when the system does From the first law of thermodynamics, the change in
work on its surroundings, i.e. when q is negative and internal energy of a system is affected by both heat and
w is negative; work, according to the equation

■ ΔU is positive when heat enters the system from its ΔU = q + w


surroundings (Ufinal > Uinitial) or when work is done on For a system in which no work is being transferred between
the system by the surroundings, i.e. when q is positive the system and its surroundings (i.e. w = 0), the internal
and w is positive. energy change will be equal to the heat absorbed or lost by
the system to its surroundings.
Work (w) Heat (q)
work done on system ΔU = q (if w = 0)
6U = + 6U = +
ΔU can therefore be found by measuring the temperature
system
work done by system change accompanying the heat loss or gain by the system
6U = – 6U = –
and the surroundings when w = 0.

surroundings How can we ensure that w = 0? In most chemical reactions,


the work we are interested in is that of expansion (PΔV).
Figure 8.5 Sign convention. The work done on the system (w) Work of expansion is given by
and the heat absorbed by the system (q) are positive as both
increase the internal energy of the system. The work done on w = −PΔV
the system (–w) and the heat lost by the system (–q) are both
Substituting this in the equation for ΔU gives
negative as both decrease the internal energy of the system.
ΔU = q + w = q − PΔV

ITQ 5 Which of the following are state functions?


(a) heat (b) work (c) pressure (d) volume
80 Unit 1 Module 1 Fundamentals in chemistry

No work of expansion will be done by the system or on the ignition wires


system therefore if there is no change in the volume of the
system (ΔV = 0). Under these conditions of constant V, the
thermometer
change in internal energy is equal to the heat lost or gained insulation
by the system.
ΔU = qV (V is constant so w = 0)
A bomb calorimeter is used to make measurements of
heat given off or absorbed during a chemical reaction at
constant volume (Figure 8.6). The chemical reactants
stirrer bomb
(the system) are placed in the calorimeter, which is then
sealed and placed in another container with a known sample holder
volume of water (the surroundings). An electric current
is passed through an ignition wire which is used to initiate water in inner container
the chemical reaction. The reaction will release heat to the
surroundings, resulting in an increase in the temperature
of the entire apparatus. The amount of heat transferred
from the system to the surroundings is determined from Figure 8.6 A bomb calorimeter.

the mass of the water, the specific heat capacity of the


water and the temperature change.
Enthalpy
q = m × c × ΔT
Most chemical reactions are done in open flasks and not
This amount of heat will be equal to the change in internal
in sealed containers at constant volume (Figure 8.7).
energy of the system since no work was done by or on the
Under these conditions, where gases can enter or leave the
system at constant volume:
system, the total pressure remains constant and equal to
ΔE = qV = m × c × ΔT the atmospheric pressure.

Worked example 8.3 thermometer stirrer

A calorimeter containing 300 g water is heated with 250 kJ of


Q heat. The temperature of the water increases from 30 °C to
80 °C. Calculate the heat capacity of the calorimeter in J °C−1.
The specific heat capacity of the water is 4.184 J g−1 °C−1.
insulated vessel
We will first calculate the heat gained by the water in the
A calorimeter. The remaining heat will be used to heat the reaction mixture

calorimeter so we can use it to determine the heat capacity of


the calorimeter.
Figure 8.7 Reactions in real life – in an open flask and not at
temperature change = 80 °C − 30 °C = 50 °C
constant volume.
heat gained by the water in the calorimeter = mass of the water
× specific heat capacity of the water × temperature change The heat change taking place under constant pressure is
heat gained by the water = 300 g × 4.184 J g−1 °C−1 × 50 °C called the change in enthalpy of the system. Enthalpy
= 62760 J = 62.76 kJ is given the symbol H and the change in heat content of
We are told that the total heat added was 250 kJ. Therefore: a system at constant pressure – the change in enthalpy – is
heat absorbed by the calorimeter = 250 kJ − 62.76 kJ written ΔH.
= 187.24 kJ In practice, a change in enthalpy is simply a change in heat
heat absorbed by the calorimeter = content and the words are used interchangeably. However,
heat capacity of the calorimeter × temperature change in thermodynamic calculations, where conditions must be
heat capacity of the heat absorbed by the calorimeter specified, it is correct only to say ‘enthalpy’. A quantity
=
calorimeter temperature change of heat energy can properly be called ‘heat’ and referred
187240 J to as ‘energy’ but a change in heat content of a system at
= = 3744.8 J °C−1
50 °C constant pressure is a change in its enthalpy.
Chapter 8 Thermochemistry 81

Enthalpy of reaction a b

Chemical reactions are classified


as exothermic if they give off Ea
heat or endothermic if they
Ea

Energy

Energy
absorb heat.
products reactants
■ When ΔH is positive,
the process is said to be 6H 6H

endothermic. Heat is
absorbed by the system and reactants products
it gains energy.
Reaction coordinate Reaction coordinate
■ When ΔH is negative,
the process is said to be Figure 8.8 Reaction profiles for (a) an endothermic reaction and (b) an exothermic reaction.

exothermic. Heat is released


from the system and it loses
energy.
The reaction between ammonium nitrate (NH4NO3) and For example, the combustion of methane gas produces
water is an example of an endothermic reaction. Some 890 kJ of heat. This reaction (thermochemical equation) is
cooling packs, used to treat sporting injuries, contain represented as:
ammonium nitrate and water – separated from each other CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = −890.4 kJ
by a thin membrane. When the membrane is broken, they
combine and the ammonium nitrate dissolves in the water. This means that the heat released when 1 mole of methane
This reaction absorbs heat from the surroundings, the pack reacts with 2 moles of oxygen to give 1 mole of carbon
gets cold and can be used in the place of ice to cool items or dioxide and 2 moles of water is 890.4 kJ. ΔH is negative
treat sport injuries. because enthalpy is lost from the system to the surroundings.
Notice that the equation specifies water in its standard
NH4NO3(s) + H2O(l) → NH4+(aq) + NO3−(aq) state (liquid) rather than as steam. The combination of
ΔH = 25.7 kJ mol−1 the balanced equation and the molar enthalpy change of
the reaction gives the thermochemical equation for the
Thermodynamic standard state enthalpy of chemical reaction.
reaction
An enthalpy change determined under standard conditions
For a given reaction the enthalpy change for the chemical
for a reaction is called the standard enthalpy of reaction,
reaction depends on the temperature, the pressure and other
ΔH (note the superscript ).
conditions under which the reaction was carried out. In order
to allow for the comparison of the results of experiments 2H2(g) + O2(g) → 2H2O(g) ΔH = −484 kJ
done under different conditions, a standard set of conditions For a given reaction, the enthalpy change of the reverse
is defined for all thermodynamic measurements. reaction has the same magnitude but the opposite sign. If
The standard state refers to a pure substance in a specified the forward reaction is endothermic, the reverse reaction
state, usually its most stable form, at 1 bar pressure, is exothermic.
at a specified temperature, usually 25 °C (298 K) and
1 mol dm−3 concentration for all substances in solution. Hess’s law
The thermodynamic standard state defines the specific The difference between the initial and final values of
physical state of reactants and set of conditions for all enthalpy does not depend on the path taken by the
chemical reactions. reaction. This conclusion was reached in 1840 by Germain
Hess (a Swiss-born Russian chemist, 1802–1850), based on
The enthalpy change that is reported for a reaction is the his experiments. A general law, now known as Hess’s law
amount of heat released when reactants are converted was proposed.
to products in the molar amounts represented in the
stoichiometric equation. Hess’s law: the enthalpy change of a reaction (ΔH ) is the
same regardless of whether the reaction occurs in one step
or several steps. The overall enthalpy change for a reaction
82 Unit 1 Module 1 Fundamentals in chemistry

is therefore equal to the sum of the enthalpy changes for M–X(g) → M(g) + X(g)
the individual steps in the reaction. H2(g) → H(g) + H(g)
If enthalpy was not a state function it would be possible These values are positive. The products contain more
for a system to change from state 1 to another state 2 via energy than the original compound.
a path requiring a certain amount of energy. If returning
from state 2 to state 1 via a different path released more The enthalpy change of atomization or enthalpy of
energy, this would mean that each time we go from state atomization, ΔHatm, is the amount of energy required to
1 to state 2 then back to state 1 we would have energy break all the bonds in a gaseous molecule into its neutral
to spare. We would have produced a device that creates gaseous atoms. ΔHatm is therefore the sum of all the bond
energy, known as a perpetual motion machine, a situation energies in the molecule. For example, ΔHatm for methane,
that is contrary to the law of conservation of energy. CH4, is the energy required for the process:

The industrial production of ammonia from hydrogen and CH4(g) → C(g) + 4H(g)
nitrogen (the Haber process) can be proposed to proceed The values are positive.
via the following hypothetical steps:
For a simple diatomic molecule, e.g. I2 or H2, ΔHatm is the
Step 1 2H2(g) + N2(g) →N2H4(g) ΔH 1 = ? same as ΔHdiss since there is only one bond between the
Step 2 N2H4(g) + H2(g) →2NH3(g) ΔH 2 = −187.6 kJ atoms.
N2(g) + 3H2(g) + N2H4(g)→ N2H4(g) + 2NH3(g) The enthalpy change of combustion or enthalpy of
Overall reaction combustion, ΔHcomb, is the energy released by 1 mole of a
3H2(g) + N2(g) →2NH3(g) ΔH reaction = −92.2 kJ given substance when it is completely burned in oxygen.

Both steps of the reaction add to give the overall reaction CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
and, according to Hess’s law, the sum of the enthalpy Values here are negative since energy is lost from the
changes for each step gives the overall enthalpy change. system.
The enthalpy changes for step 2 and the overall reaction The enthalpy change of neutralization or enthalpy of
are known. However, it is difficult to measure the enthalpy neutralization, ΔHneut, is the energy released when 1 mole
change for step 1. The enthalpy change for step 1 can be of an acid or base is completely neutralized. For all strong
calculated using Hess’s law as follows: acids or bases, its value is approximately −57.5 kJ mol−1.
ΔH reaction → ΔH 1 + ΔH 2 The enthalpy change of fusion (melting) or enthalpy
ΔH 1 = ΔH reaction − ΔH 2 = +95.4 kJ of fusion, ΔHfus, is the energy required to melt 1 mole of a
substance at its melting point to give the liquid at the same
Rules for applying Hess’s law temperature.
■ If a reaction is reversed, the sign of ΔH must be reversed.
M(s) → M(l)
■ If the reaction is multiplied or divided by a factor, ΔH
must also be multiplied or divided by the same factor. Values are positive.
The enthalpy change of vaporization or enthalpy
Examples of enthalpy changes of vaporization, ΔHvap, is the energy required to convert
There are special terms assigned to enthalpy changes 1 mole of a substance from the liquid to the gas phase at
for particular types of chemical reactions and physical the same temperature.
processes. We will use the convention that if heat energy M(l) → M(g)
is lost from the system, the value of the change is negative
and if heat energy is gained by the system, its value is Values are positive.
positive. Tables of values supplied in other books and on The enthalpy change of sublimation, ΔHsub, is the
the internet do not always use this convention, so be sure energy required for the sublimation of 1 mole of a substance
that you get the signs (+ or –) right from solid to gas at the same temperature.
The enthalpy change of bond dissociation or bond ΔHsub = ΔHfus + ΔHvap
dissociation enthalpy, ΔHdiss, is the amount of energy
Values are positive.
required to break a chemical bond in 1 mole of an isolated
molecule in the gaseous state.
Chapter 8 Thermochemistry 83

The enthalpy change of hydration or heat of solution, Lattice enthalpy


ΔHhyd, is the energy change during the hydration of 1 mole
The lattice enthalpy, ΔHlat, is the heat energy given out
of a gaseous ion.
when 1 mole of a substance is formed from its gaseous ions.
Na+(g) + water → Na+(aq)
Na+(g) + Cl−(g) →NaCl(s)
This can be positive (if heat is released) or negative (if heat
Lattice enthalpy depends on:
is absorbed).
■ the charges on the ions;
The enthalpy change of solution or heat of solution,
■ the distance between the ions.
ΔHsoln, is the energy change when 1 mole of a substance is
dissolved in a solvent at infinite dilution, e.g. water. The lattice enthalpy is proportional to the product of the
charges on the ions. The greater the charge on the ions, the
NaCl(s) + water → NaCl(aq) or
greater is the attraction between the ions and the greater is
NaCl(s) + water → Na+(aq) + Cl−(aq) the lattice enthalpy. For a given set of ions of similar size,
The value can be positive if the solution absorbs heat the lattice enthalpy is greatest for the most highly charged
energy or negative if heat energy is released. ions. The lattice enthalpy of a compound with charges
M2+X2− is grater than one with M+X−. As an example, the
In order for a substance to dissolve in a solvent, energy must
lattice enthalpy of LiCl is less than the lattice enthalpy of
be supplied to the ions in the substance to separate them
MgCl2.
from each other (ΔHlat). The ‘free’ ions are then solvated/
hydrated (surrounded by solvent) due to electrostatic The lattice enthalpy is inversely proportional to the distance
attraction between the solvent and the ions. If the solvent between the ions. So for compounds with the same charges
is water, these interactions could be hydrogen bonding, on their ions, the smaller the distance between the ions, the
ion–dipole interactions or dipole–dipole interactions. This greater is the attraction between the ions and the greater
is discussed further below. is the lattice enthalpy. For example the lattice enthalpy
increases in the order
The enthalpy change of solution is therefore the sum of
the lattice enthalpy of the compound and the hydration NaF > NaCl > NaBr > NaI
enthalpies of the ions. For example: LiF > LiCl > LiBr
NaCl(s) + water → Na +(aq)
+ Cl−(aq) ΔHsoln(NaCl) LiF > NaF > KF
Na+(g) + water → Na+(aq) ΔHhyd(Na+)
−(g) + water → Cl−(aq) ΔHhyd(Cl−)
Cl Calculating enthalpy changes
NaCl(s) → Na+(g) + Cl−(g) ΔHlat(NaCl)
The standard enthalpy of formation is the enthalpy
+ −
ΔHsoln = ΔHhyd(Na ) + ΔHhyd(Cl ) + ΔHlat(NaCl)
change ΔH f for the formation of 1 mole of a substance
The enthalpy change of first ionization, ΔHIE1, is the in its standard state from its constituent elements in their
energy required during the removal of an electron from standard (or reference) states (pressure = 1 bar and 25 °C/
1 mole of a gaseous atom. 298 K).
Na(g) → Na+(g) + e− The reaction to form a substance from its elements is
Values are positive. hypothetical. This definition gives a reference level from
which all changes are measured. Each substance involved
The enthalpy change of electron gain (or electron in the reaction must be in its standard state: usually
affinity), ΔHea, is the energy change during the addition of the most stable form at 1 bar pressure and the specified
an electron to 1 mole of a gaseous atom. temperature (usually 298 K).
Cl(g) + e− → Cl−(g) The standard enthalpy change for any chemical reaction is
If heat energy is released during this process then the value the difference between the sum of the heats of formation
is negative. If heat energy is absorbed then the value is of all reactants and the sum of the heats of formation of all
positive. First electron affinities are negative, but many products:
data tables quote them as positive values. ΔH reaction → ΔH f (products) − ΔH f (reactants)
84 Unit 1 Module 1 Fundamentals in chemistry

Consider the general reaction: The Born–Haber cycle


aA + bB + … → cC + dD + … The Born–Haber cycle is a method of assessing the
ΔH reaction = [cΔH f (C) + dΔH f (D) + …] stability of ionic compounds. The application of Hess’s law
− [aΔH f (A) + bΔH f (B) + …] can be extended to calculating the overall energy change
for the formation of ionic crystals.
Now consider the reaction:
We can get an indication of the stability of a compound
CO(g) + ½O2(g) → CO2(g) ΔH reaction = ? kJ from its standard enthalpy of formation (ΔH f ). If ΔH f
The hypothetical steps for this reaction are as follows: is negative, the formation reaction is exothermic and the
compound formed is stable and likely to be formed.
Step 1
C(s) + ½O2(g) → CO(g) ΔH f (CO) = −110 kJ mol−1 Combining solid Na with gaseous Cl2 results in a violent
reaction and NaCl solid is produced, as well as a great
Step 2
amount of heat. The equation for this reaction is:
C(s) + O2(g) → CO2(g) ΔH f (CO2) = −393.5 kJ mol−1
Na(s) + ½Cl2(g) → NaCl(s) ΔH f = −411 kJ mol−1
Step 3
O2(g) → O2(g) ΔH f (O2) = 0 kJ mol−1 The question we need to ask is: ‘Why is the formation of
NaCl so favourable?’
In accordance with the general formula given above, we get:
If we look at the enthalpy changes for the electron transfer
ΔH reaction = ΔH f (CO2) − [ΔH f (CO) + ΔH f (O2)]
process only, we will see that this is not an exothermic
ΔH reaction = −393.5 kJ mol−1 − process. To get a better picture of the reaction between
[(−110 kJ mol−1) + (0 kJ mol−1)] Na and Cl2, we can consider all the steps that might be
= −283.5 kJ mol−1 involved. If the enthalpy changes for each of these steps are
known then we can apply Hess’s law. The sum of enthalpies
Using bond dissociation energies of these individual steps should be equal to the formation
For reactions where ΔHf values are not available, it is enthalpy of NaCl.
possible to get approximate values for enthalpy changes by The reaction is between solid Na and Cl2 gas so, before
using average bond dissociation energies (ΔH diss ). an atom of Na can combine with an atom of Cl, it must
Bond dissociation energies are always positive, as energy first be separated from other atoms to which it is bonded.
must be supplied to break a chemical bond. For example, That is, in the solid metallic Na there are several Na atoms
the standard enthalpy change for the reaction Cl2(g) → bonded to each other and in the gas Cl2 there are Cl atoms
2Cl(g) is +243 kJ mol−1: bonded to each other as molecules. One way of separating
the atomic interactions in each reactant is by taking them
Cl–Cl → 2Cl ΔH diss = +243 kJ mol−1 to the gas phase. Once the atoms are separated the process
ΔH diss can be abbreviated to D. of ionization can occur through electron transfer and the
charged species once formed will attract each other to form
By application of Hess’s law, it is possible to calculate
the crystal. These steps are summarized below and values
an approximate enthalpy change for any reaction by
for their enthalpy changes are given: The overall energy
subtracting the total energy of bonds formed in the products
change, ΔH reaction , is calculated by considering the series of
from the total energy of bonds broken in the reactants.
steps:
ΔH reaction = ∑D(bonds broken) − ∑D(bonds formed)
1: enthalpy of sublimation Na(s) → Na(g) ΔH sub = +107.3 kJ mol
−1
Let’s look at an actual reaction:
2: bond dissociation enthalpy ½Cl2(g) → Cl(g) ΔH diss = +122 kJ mol
−1

H2(g) + Cl2(g) → 2HCl(g) 3: enthalpy of ionization Na(g) → Na+(g) + e− ΔH IE1 = +495.8 kJ mol−1

Bonds broken: H–H(g) and Cl–Cl(g) 4: enthalpy of electron affinity Cl(g) + e− → Cl−(g) ΔH ea = −348.6 kJ mol−1
5: lattice energy Na+(g) + Cl−(g) → NaCl(s) ΔH lat = −787 kJ mol−1
Bonds formed: 2H–Cl(g)
6: ΔH reaction Na(s) + ½Cl2(g) → NaCl(s) = −411 kJ mol−1
ΔH reaction = [D(H2) + D(Cl2)] − (2D(HCl)]
= (243 kJ + 436 kJ) − (2 × 432 kJ) ITQ 6 The enthalpy change of combustion of acetylene gas,
C2H2, at 25 °C is 310.5 kJ mol−1. Work out the enthalpy of
= −185 kJ
formation of acetylene gas.
Chapter 8 Thermochemistry 85

The five steps that are involved


in the formation of sodium 1st ionization: Na(g) Na+(g) + e– –348.6 kJ mol –1 electron affinity: Cl(g) + e– Cl –
chloride, and the overall energy
495.8 kJ mol –1
change, can be represented in
a thermochemical cycle called
a Born–Haber cycle. The Born– bond dissociation:
1
2 Cl2(g) Cl(g)
122 kJ mol –1
Haber cycles for the formation of
sodium chloride and magnesium sublimation: Na(s) Na(g)
107.3 kJ mol –1
chloride are shown in Figures 8.9
1 lattice energy
and 8.10. Na(s) + 2 Cl2(g)
–1
–787 kJ mol
The enthalpy changes for steps 3
and 4 are the ionization energy net reaction
–411kJ mol –1
and electron affinity respectively.
Note that all the steps except 4
and 5 are endothermic processes.
In fact, if the enthalpy changes NaCl(s)
for the steps up to the formation
Figure 8.9 The Born–Haber cycle for NaCl.
of the gaseous ion (steps 1–4)
are combined, a value of ΔH
= +376.2 kJ mol−1 is obtained, 2nd ionization: Mg+(g) Mg 2+(g) + e – –697.2 kJ mol –1 electron affinity: 2Cl(g) + 2e – 2Cl –

indicating that that the formation


1450.7 kJ mol –1
of gaseous (free) ions from solid
Na and gaseous Cl2 is an overall
endothermic process. The addition
of the last step (step 5), where the 1st ionization: Mg(g) Mg+(g) + e– 737.7 kJ mol –1 lattice energy
ions attract each other to form the –2524 kJ mol–1
lattice (crystalline network), make
bond dissociation: Cl 2(g) 2Cl(g) 243 kJ mol –1
the overall process exothermic.
One can conclude therefore that sublimation: Mg(s) Mg(g)
147.7 kJ mol –1
the major contributing factor to
Mg(s) + Cl2(g)
the stability of NaCl is the strong
force of attraction between the net reaction

ions that give rise to the formation Mg(s) + Cl2(g) MgCl2(s)


–642 kJ mol –1
of the crystal (ΔH lat ).
MgCl2(s)
The enthalpy of formation is
Figure 8.10 The Born–Haber cycle for MgCl2.
therefore the sum of all the
enthalpy changes for the steps
listed.
ΔH f = ΔH vap + ΔH diss + ΔH sub + ΔH IE1 + ΔH ea + ΔH latt
The enthalpy of formation of an ionic compound can be the agreement is poor that one can conclude that there
determined experimentally and the value compared to might be some other type of bonding occurring, perhaps
that obtained theoretically using Hess’s law. Similarly, covalent. Tables 8.2–8.4 show some values obtained for
lattice energy values can be obtained from Hess’s law theoretical and experimental values of lattice enthalpy for
calculations as well as from a theoretical equation. If there some compounds. NaCl shows excellent agreement and
is good agreement between the value calculated from the is therefore a good model of almost pure ionic bonding.
Born–Haber cycle and that obtained experimentally, then For AgCl, which is larger, the discrepancy is greater due to
one can say that the ionic model of bonding proposed greater polarizability of the ions resulting in more covalent
is a good one for the compound under consideration. If character in this compound.
86 Unit 1 Module 1 Fundamentals in chemistry

Table 8.2 Lattice enthalpies for Group I halides


Compound ΔH lat / kJ mol−1 Compound ΔH lat / kJ mol−1 Compound ΔH lat / kJ mol−1 Compound ΔH lat / kJ mol−1
LiF 1037 LiCl 852 LiBr 815 LiI 761
NaF 936 NaCl 787 NaBr 747 NaI 705
KF 821 KCl 717 KBr 689 KI 649

Table 8.3 Lattice enthalpies for some other ionic compounds


Compound ΔH lat / kJ mol−1 Compound ΔH lat / kJ mol−1 Compound ΔH lat / kJ mol−1 Compound ΔH lat / kJ mol−1
MgO 3850 CaO 3461 SrO 3283 BaO 3114
MgS 3406 CaS 3119 SrS 2974 BaS 2832
Al2O3 15900

Table 8.4 Theoretical and experimental values of ΔH lat in kJ mol−1 for some compounds
Compound ΔH lat / kJ mol−1, theoretical ΔH lat / kJ mol−1, experimental
NaCl −769 −787
NaBr −732 −747
AgCl −830 −904

Summary
✓ Thermochemistry is the branch of ✓ A state function is a property whose value
thermodynamics that focuses on the energy depends only of the present state of the system
changes that occur during chemical and physical and not on the path taken to arrive at that state.
processes. Internal energy, temperature and pressure are
state functions.
✓ A system can transfer energy to its surroundings
in the form of heat that can be measured in ✓ Enthalpy change is the heat change in a system
terms of temperature changes. at constant pressure.

✓ The total energy of the system and its ✓ Hess’s law states that the overall enthalpy
surroundings is, however, constant. When a change for a reaction is equal to the sum of the
system expands, the sign of the work done is enthalpy changes for the individual steps in
negative and when the system contracts, the the reaction. Application of Hess’s law allows
work done has a positive sign. for the determination of enthalpy of formation
of reactions from enthalpy changes for other
✓ The heat given off or absorbed by a closed system
related reactions.
at constant volume can be measured using a
bomb calorimeter. ✓ Bond dissociation enthalpies can be used to
calculate enthalpy of formation for a compound.
✓ Reactions that give off heat are exothermic and
those that absorb heat are endothermic.
Chapter 8 Thermochemistry 87

Review questions 8 From ΔHcomb values for methane, ethane and propane
(which are −885.4, −1547.3 and −2210.5 kJ mol−1,
1 50 cm3 of 1.0 mol dm−3 HCl at 30 °C at was mixed
respectively) estimate the increase in ΔHcomb per
with 50 cm3 of 1.0 mol dm−3 NaOH at 30 °C in a
added CH2 group in a hydrocarbon. Predict ΔHcomb
Styrofoam calorimeter. The temperature of the
for octane on this basis, and compare this value to the
calorimeter rose by 4.5 °C. Calculate the heat of
usually accepted value of −5468 kJ mol−1.
reaction per mol of H2O(l) formed. (The heat capacity
of the calorimeter is 50 J °C−1.) 9 The heat released on neutralization of NaOH with all
strong acids is 56.2 kJ mol−1. The heat released on
2 15.0 g of methanol (CH3OH) was burned in a
neutralization of NaOH with HF (a weak acid) is
bomb calorimeter containing 2.40 kg of water. The
68.9 kJ mol−1. Calculate ΔH for the ionization of HF
temperature of the water and calorimeter rose from
in water.
35.00 to 38.10 °C. The specific heat capacity of water
is 4.18 J g−1 K−1. Assuming negligible heat loss to the
Answers to ITQs
calorimeter, determine:
(a) the amount of heat evolved in the reaction; 1 (a) chemical energy to electric energy and vice versa
(b) the molar heat of combustion for methanol. (b) heat energy to kinetic energy
(c) chemical energy to heat energy
3 Determine the heat of reaction for the following
combustion: 2 Effect of oceans moderating the weather, cooling of
C3H7COOH(l) + 5O2(g) → 4CO2(g) + 4H2O(l) our bodies when we perspire.
Use this data: 3 Aluminium since it requires less heat to change its
4C(s) + 4H2(g) + O2(g) → C3H7COOH(l) ΔH = −522 kJ temperature by 1 °C.
C(s) + O2(g) → CO2(g) ΔH = −392.9 kJ 4 The water freezes on the cold branches, releasing
2H2(g) + O2(g) →2H2O(g) ΔH = −241.6 kJ latent heat. This raises the temperature of the blossom
H2O(l) → H2O(g) ΔH = 43.9 kJ sufficiently to preserve it from the intense cold.

4 Calculate the enthalpy change of formation for MgO, 5 Work is not a state function since it depends on the
ΔHf(MgO(s)) given the following data: distance travelled, which depends on the path taken
MgCO3(s) → MgO(s) + CO2(g) ΔH = 117 kJ from the initial to final state. Heat also depends on
the path taken so it not a state function. Pressure and
ΔHf(MgCO3(s)) = −1113 kJ mol−1
volume are state functions.
ΔHf(CO2(g)) = −394 kJ mol−1
6 54.2 kJ mol−1
5 Given the following information:
ΔH f (SO2(g)) = −297 kJ mol−1 Answers to Review questions
ΔH f (CaO(s)) = −635.5 kJ mol−1
1 42.2 kJ mol–1
ΔH f (CaSO4(s)) = −1433 kJ mol−1
2 (a) –31.09 kJ
Calculate the enthalpy change for the reaction:
(b) –66.3 kJ mol–1
CaSO4(s) → CaO(s) + SO2(g) + ½O2(g)
3 –1708.4 kJ
6 Name the enthalpy changes for the following processes:
(a) H2O(s) → H2O(l) 4 –602 kJ mol–1
(b) I2(s) → I2(g) 5 500.5 kJ
(c) 2K(s) + Cl2(g) → 2KCl(s)
6 (a) fusion
(d) C3H8(g) + O2(g) → 3CO2(g) + 4H2O(l)
(b) sublimation
7 Calculate the heat produced when 1.00 gal of octane, (c) formation
C8H18, reacts with oxygen to form carbon monoxide (d) combustion
and water vapour at 25 °C.
7 15 520 kcal
Data: density of octane = 0.7025 g cm−3;
8 –5522.5 kJ
1 gal = 3.785 dm3, ΔHcombustion(C8H18) = −1302 kcal
9 –12.7 kJ
88

Module 2
Kinetics and equilibria

Chapter 9
Chemical kinetics
Learning objectives
■ Explain what is meant by the rate of a reaction.
■ Apply the collision theory to explain factors affecting reaction rate.
■ Use the concept of a Boltzmann distribution in reaction rates.
■ Understand the information contained within a reaction profile.
■ Explain what is meant by the order of a reaction.
■ Distinguish between first-order and pseudo first-order reactions.
■ Explain what is meant by a reaction half-life.
■ Describe how to find the order of a reaction from experimental data.

Collision theory (movement from place to place). For a massive particle,


such as an atom or molecule, the movement energy
Is there a way to explain why some reactions, such as (kinetic energy) is the largest component. The magnitude
explosions, are fast and some, like the rusting of an old car, of kinetic energy is given by
are slow?
1 2
KE = mv
You need to remember that matter is made of particles. These 2
particles may be atoms, ions, molecules, micelles, colloidal where KE is the kinetic energy, m the mass and v the
dispersions or anything else. What ever the particle, there velocity.
are only two ways in which a reaction can happen: We can show that for an ideal monatomic gas
■ a particle can absorb energy (as heat, light or UV 3
KE = kT
energy) and split apart; 2
■ two particles can collide, making fragments which where T is the absolute temperature (in kelvin) and k is a
recombine either in the same form or as something constant. Ideal gases are introduced in Chapter 7.
different. Combining the two equations gives
The second of these possibilities is the more common. 1 2 3 –
mv = kT , so v ∝ √T
We can set up a general chemical reaction: 2 2
As the temperature rises, the particles rush around more
AB + CD → AC + BD quickly. This applies in general to all particles, not just the
Now we can ask what factors are at work to regulate it. atoms of an ideal gas.

Internal energy Bond energy


At any temperature above absolute zero, particles (whatever We can widen the argument to consider molecules. When
they are) contain movement energy. This movement the atoms or ions making up the molecule came together,
energy can be in the form of vibration, spin or translation they stayed together because a bond formed between
Chapter 9 Chemical kinetics 89

them. Another way of saying this is that in the ‘together’ If the energy available in the collision is below ΔE there can
state, the molecule contained less energy than when its be no reaction.
constituents were separate. When bonds are formed, the If the energy is above ΔE then the reacting particles are
energy content of the system falls. separated into their components and at that moment there
To split the particle up again, an equal amount of energy is an intermediate state containing reactive fragments:
must be supplied. AB + CD → A + B + C + D

Collision effects At this point either the fragments will recombine, giving
the original reactants, or they will change partners and
Not all collisions will have the same energy. In a fluid (gas
combine giving the new materials AC and BD.
or liquid) at a fixed temperature, some particles are moving
slowly, most rather more quickly and some very quickly.
Product stability
This distribution of energies, known as the Boltzmann
distribution, is shown in Figure 9.1. We only say that a reaction has taken place if noticeable
amounts of AC and BD are produced. This happens if (AC
+ BD) is more stable than (AB + CD); this is the case if the
energy released in forming AC and BD is greater than the
Number of molecules

energy released in recombining the original AB and CD.

Effect of molecular shape


If the reacting particles are spherical it does not matter
which way they collide. If the particles have a reactive site
Energy 6E (for example, the –OH group in an alcohol) then the other
Figure 9.1 Particle energy (x-axis) against number of particles reagent must strike that site. The proportion of fruitful
having that energy (y-axis). collisions goes down.
Most particles have an energy near to the red line. The
number of particles having an energy greater than a value Reaction rate
such as the dotted line is proportional to the area under We have a verbal scale for reaction speed. We can say ‘doesn’t
the curve to the right of that line, as shown by the shaded react’ or ‘slow’ or ‘fast’ or ‘explosive’. However, we can also
portion. measure the change in a reaction by measuring the change
If the proportion of collisions with enough energy to cause in quantity of a reactant or product over time. In this case
a reaction goes up, the number of fruitful collisions per we will record our results in mol s−1. We can also measure
second goes up and the reaction proceeds more quickly. some physical property of the reaction mixture, such as the
In a gas, or in a solution, the particles are moving largely volume of a gas evolved, or the depth of colour or the pH.
independently of each other. They move in straight lines Because the majority of reactions only take place when
except when they bounce off the walls of the container particles collide, anything that changes the effective collision
or into each other. When they collide, the sum of their frequency between particles will affect the reaction rate.
available energies can either be sufficient to split up the Factors to consider are:
molecules into fragments, or insufficient to do so. We can
show this energy as the value ΔE. ■ concentration of a solution or the pressure of a gas;
■ temperature;
■ surface area of a solid;
ITQ 1 What might happen if the collision energy was enough to
split up AB but not enough to split up CD? ■ use of a catalyst.

Concentration
ITQ 2 Why are inorganic reactions usually faster than organic
reactions? If the concentration of a reactant is increased, the rate of
reaction may also increase. If we use the simple collision
theory outlined above, we could say that the reacting particles
ITQ 3 What property of a gas do we use to express its
concentration? are crowded together more, so they collide more often.
90 Unit 1 Module 2 Kinetics and equilibria

Experiments show that for the reaction This reaction is first order with respect to both 2-bromo-2-
A+B→X+Y methylpropane and to water and so is second order overall
(see below). But if the water is present in a large excess
one factor controlling the reaction rate is the concentration (as the solvent) then its concentration does not change
of the reactants: appreciably and the rate equation becomes
rate = k [A] [B] rate = k [(CH3)3CBr]
However, the reactants may not react in a simple way. In The reaction now appears to be first order – hence the term
practice, the general rate equation is: ‘pseudo’ first-order.
rate = k [A]a [B]b
Second-order reactions
where a and b are small numbers, usually 0, 1 or 2. The There are two types of second-order reactions:
constant k is called the rate constant for that reaction.
■ those in which two different species react together, the

Order of reaction reaction being first order with respect to each;


■ those where there is only one reactant in the rate
The integers a and b in the rate equation define the order
equation, but the reaction is second order with respect
of the reaction. In our example, the reaction is of order
to that species.
a with respect to A, and of order b with respect to B. The
An example of the first type is the alkaline hydrolysis of an
overall order is (a + b).
ester such as ethyl ethanoate:
First-order reactions
CH3COOC2H5 + OH− → CH3COO− + C2H5OH
Consider the reaction
For this reaction, the rate equation is
A → products
rate = k [CH3COOC2H5] [OH−]
The rate equation is found to be
Notice that because only one mole of each reactant is
rate = k [A] involved in the change, each term in the equation is only
Suppose that after a certain time t the rate has fallen to ½ to the first order.
the original value. After another interval t the rate will be An example of the second type, where there is only one
½ × ½ = ¼ and so-on. The time for the rate to reduce by a reactant, is the decomposition of nitrogen dioxide:
factor of 2 is called the half-life of the reaction. Radioactive
2NO2 → 2NO + O2
decay proceeds in this way (see Chapter 3).
rate = k [NO2]2
Worked example 9.1 Here, because the reactant appears to the second order in
the chemical equation for the reaction, a first suggestion
The half-life of tritium (3H) is 12.3 years. A sample is decaying
Q at the rate of 1000 atoms per second. How long will it be would be that the corresponding term in the rate equation
before the decay rate is only 125 atoms per second? is squared.
You could write the reaction as
A 125 1 1 1 1
= = × × so three half-lives are needed.
1000 8 2 2 2 NO2 + NO2 → 2NO + O2
Half-life is 12.3 years, so decay will take 3 × 12.3 = 36.9 years This link between the chemical equation for the reaction
and the rate equation is true of any single-step reaction.
However, you must be aware that many reactions take
Pseudo first-order reactions place in a series of steps; if this is the case then the order of
When a reagent is present in considerable excess, its the reaction can only be found by experiment – which is
concentration does not change appreciably during the discussed later in this chapter (page 93).
reaction, and so the order with respect to that reagent is
effectively zero.
Consider the reaction ITQ 4 If the reaction between (CH3)3CBr and H2O is performed
with methanol as the solvent instead of water, suggest the rate
(CH3)3CBr + H2O → products equation for the reaction.
Chapter 9 Chemical kinetics 91

Zero-order reaction transition state

There are two types of reaction that appear to be


independent of the pressure or concentration of a reactant.

Potential energy
Ea
The first type is a gas reaction catalysed by a metal surface.
In the reaction
2NH3 → N2 + 3H2
reactants 6H
on a molybdenum catalyst, the surface of the catalyst
becomes covered with ammonia molecules whatever the
Reaction coordinate
gas pressure. Therefore the reaction rate is independent of
the gas pressure. Figure 9.2 A reaction profile for an exothermic reaction showing
the activation energy (Ea). The y-axis shows the potential energy
An example of the second type is the reaction between of a pair of reactant particles. The x-axis shows the course of the
iodine and acetone (propanone). reaction, which is called the reaction coordinate.

CH3COCH3(aq) + I2(aq) → CH2ICOCH3(aq) + HI(aq) For a reaction to take place, a collision must provide energy
The rate of this reaction does not change if the concentration equal to, or greater than, the energy at the peak of the
of the iodine is changed. The reaction is said to be zero profile. This energy (Ea) is called the activation energy of
order with respect to iodine. This tells us nothing about the the reaction.
order of reaction overall. If the temperature is increased we can see from the diagram
Never assess the order of a reaction from the equation of the Boltzmann distribution that a higher percentage of
alone. Dinitrogen oxide decomposes to give nitrogen and particles will have more than a particular amount of energy,
oxygen: and therefore the percentage of collisions with more than
the activation energy will also be higher (Figure 9.3).
2N2O → 2N2 + O2
but the reaction is first order. This is because many reactions
Number of molecules

take place in stages, through intermediates, and one stage


may be slower than others and so dominate the kinetics.

Temperature
Increasing the temperature of a reaction has two effects:
■ the energy of the particles is increased, so the Energy E

proportion of the collisions that offer equal or more


Figure 9.3 The Boltzmann distribution, showing the effect of
than the activation energy of the reaction increases raising the temperature of a fixed number of particles. The
(activation energy is discussed in detail below); red line represents the Boltzmann distribution at a higher
■ the reacting particles travel faster and therefore collide temperature. The area under the red line to the right of the
activation energy (Ea) is greater than the green shaded area. The
more frequently. hotter substance has a higher proportion of particles with more
We can draw an energy profile for a reaction (Figure 9.2). than the activation energy.
This type of graph shows the potential energy of a colliding
pair of reactant particles. Initially much of the energy is Catalysis
kinetic energy, but as the reactant particles approach A catalyst is a substance that speeds up a reaction without
each other that energy is converted to potential energy itself being used up in the process. A catalyst may act by
to overcome the repulsion of the electron clouds. This forming an intermediate product or by providing a surface
potential energy reaches a maximum at the point where on which reacting molecules can come together. In either
the old bonds are breaking and the new bonds are forming. case, the catalyst does not lower the activation energy of
This is called the transition state. the reaction: it gives an alternative reaction path with a
lower activation energy (Figure 9.4).

ITQ 5 In Figure 9.3, what is the relationship between the total


area under the green line and the total area under the red line?
92 Unit 1 Module 2 Kinetics and equilibria

transition state astonishing efficiency at or near room temperature and


at the pH of the living organism of which they form
Ea part. Enzymes are highly specific. For example, human
Potential energy

saliva contains amylase, which catalyses the conversion


of starch into sugars but has no other effect.
Enzyme molecules are coiled up into specific shapes.
reactants 6H
One theory for their action, and for their specificity, is
that the enzyme and reagent molecules come closely
together, and the shape of the enzyme molecule fits
Reaction coordinate
neatly onto the active part of the reactant molecule. This
Figure 9.4 The reaction profile for a reaction. The green line shows is called the lock-and-key mechanism (Figure 9.5).
the uncatalysed reaction and the red line the catalysed reaction.
The final energy of the system is unchanged but, since Ea is lower Enzymes can be very effective: one enzyme working in
in the presence of the catalyst, more collisions will be fruitful. the replication of a DNA molecule not only catalyses a
polymerization, but checks that the resultant polymer
Examples of catalysis
molecule is correct.
■ Dilute acid catalysing the hydrolysis of an ester
substrate
(Chapter 25, page 205):
CH3CH2CH2COOC2H5 + H2O → CH3CH2CH2COOH + C2H5OH
ester acid alcohol
The acid provides a high concentration of protons
(H+), which are the catalyst. This reaction takes place
in solution. There is only one liquid phase, and so the enzyme ES complex
effect is called homogeneous catalysis.
Figure 9.5 An enzyme fits directly onto a reactant – known as the
■ Finely divided nickel metal (‘Raney nickel’). The metal substrate – to form an intermediate complex in a reaction.
is actually an alloy of nickel and aluminium, from
which much of the aluminium has been dissolved Catalyst poisoning
out. The nickel remains as a spongy mass with a high Many catalysts, particularly heterogeneous catalysts,
surface area. A spoonful of Raney nickel has a surface become much less active in the presence of oxygen or
area of about 100 m2. sulfur compounds. It is likely that the oxygen or sulfur
Raney nickel is used to catalyse the hydrogenation of compounds bond to the catalyst surface and so prevent it
vegetable oils, converting C=C bonds to –C–C– bonds from working. This is called catalyst poisoning.
and so turning the liquid oil into solid materials such as In the Haber process for the production of ammonia,
margarine. methane (CH4) is used as the source of hydrogen. The
The metal surface combines with both the double- methane is first cleaned of hydrogen sulfide. Then the
bonded molecule and the hydrogen to give an hydrogen needs to be cleaned of the carbon monoxide
intermediate; the molecules then react together. produced in the first stage of the process:
In this example, more than one phase (liquid, solid or CH4 + H2O → CO + 3H2
gas) is present and the process is called heterogeneous Both hydrogen sulfide and carbon monoxide are powerful
catalysis. catalyst poisons.
The conversion of nitrogen and hydrogen into ammonia
Unusual catalytic effects
in the Haber process is similar, using an iron catalyst
(see Chapter 37, page 372). Strangely, some catalysts reduce the rate of reactions,
which contradicts the definition of a catalyst! How can this
■ Platinum metal is used in motor car exhausts to make
happen? When two catalysts are added to a reaction mixture
possible the conversion of nitrogen oxides (NOx) and they are usually more effective than one alone. But if one
carbon monoxide into nitrogen and carbon dioxide. catalyst happens to form an intermediate compound which
■ Enzymes are proteins – long, linear chains of amino reacts more slowly, then the other catalyst accelerates the
acids that fold to produce a three-dimensional formation of this unwanted intermediate and the reaction
product. They act as biological catalysts and work with slows down.
Chapter 9 Chemical kinetics 93

Some reactions produce their own catalyst as they proceed. Rate measurements
For example permanganate ions (MnO4−) are slowly
The rate of a reaction is found from a graph of concentration
reduced by oxalic acid to near-colourless Mn2+ ions. The
(or pressure of a gas) against time. The slope of this graph
reaction is catalysed by Mn2+ ions, so as they are formed
at any time is the rate of change at that time. From such
in a permanganate/oxalic acid mixture, the reaction rate
a graph we can derive a plot of rate against concentration
increases progressively.
of a reactant. Also, the shape of the graph can tell us the
order of the reaction with respect to that substance. If the
Light-induced reactions
substance is a reactant, its concentration falls with time
At the beginning of the chapter, we said that most reactions (Figure 9.6). If it is a product, its concentration rises.
proceed through collision. Some reactions, however, take
place differently in the dark and in sunlight. A glass flask
filled with a mixture of equal parts of hydrogen gas and
chlorine gas is stable at room temperature in a dark room. 6A
Throw the flask out through the window into the sunlight

A / mol dm–3
and it will explode before it hits the ground.
The photons (energy packets) of UV light carry enough
energy to split chlorine molecules into atoms:
Cl–Cl → Cl + Cl
Time / s t
The two electrons of the Cl–Cl bond are shared equally
Figure 9.6 Calculating the rate of a reaction.
between the two atoms. We show this by using dots for the
electrons, so the reaction is better written as: Follow the steps to find the order of a reaction.

Cl–Cl → Cl• + Cl• ■ Draw a graph of concentration of reagent against time.


■ Draw a tangent to the curve at a selected time. You can
The fragments carrying the odd number of electrons are
use t = 0 to find the initial rate.
called free radicals. Free radicals are very reactive and a
chain reaction is set up: ■ Use the tangent as the hypotenuse of a triangle that
cuts both axes.
H–H + Cl• → HCl + H•
■ Divide the value of [A] at the point where your
H• + Cl2 → HCl + Cl• and so on tangent intercepts the axis by the corresponding value
of t.
Determining the order of reaction Δ[A]
■ This gives you , the rate of reaction.
t
Think about our general reaction: ■ You can repeat this for various values of t, to draw
A + B → products another graph showing the variation of rate with time
It seems that this is likely to be a second-order reaction ■ Alternatively, you can repeat the experiment several

with a rate equation times, starting with different concentrations of


reagent, and use the initial reaction rates to draw
rate =k [A]a [B]b, where a and b can be 0, 1, 2 …
a graph showing the variation of rate with reagent
■ However, as we noted above (page 90), the order of concentration.
reaction does need to be determined by experiment:
■ if changing the initial concentration of A between two
experiments does not change the initial rate, then
a = 0 and the reaction is zero order with respect to A;
■ if doubling the initial concentration of A doubles the
initial reaction rate, then a = 1 and the reaction is the
first order with respect to A;
■ if doubling the initial concentration of A quadruples
ITQ 6
the initial reaction rate, then a = 2.
Δ[A]
What are the units of [A] and ?
t
94 Unit 1 Module 2 Kinetics and equilibria

Worked example 9.2


This data was derived from an experiment in which a reagent A Table 9.1 Step 1, the raw data
Q was progressively used up. Calculate the order of the reaction Time /s Concentration of A / mol dm−3
with respect to A. 0 1.0
5 0.84
10 0.71
15 0.59
20 0.5
25 0.42
30 0.35
40 0.25
45 0.21

Table 9.1 gives data on how the concentration of A alters with


A time. Plotting this data gives Figure 9.7.
1.2

Tangents are drawn on Figure 9.7 when the concentration 1.0


of A is 1, 0.6 and 0.2 mol dm−3.

Concentration of A / mol dm–3


0.8

0.6

0.4

0.2

0
0 20 40 60
Time / s

Figure 9.7 Step 2, plotting the data and drawing the tangents.
Data from the tangents is collected in Table 9.2.

Table 9.2 Step 3, data derived from Figure 9.7 and plotted
on Figure 9.8.
Concentration Rate
1 0.035
0.6 0.022 0.040
0.2 0.007
0.035
■ Step 1 shows the raw data.
0.030
■ Step 2 shows the concentration versus time graph with
some tangents drawn. 0.025
■ Step 3 shows the values of the rates and concentrations.
Rate

0.020
■ Step 4 shows the rate versus concentration graph.

The graph in Figure 9.8 is very nearly a straight line. The 0.015
deviation might be because:
0.010
■ the original data is not quite accurate;

■ data is only given to two significant figures; 0.005

■ the tangents were not easy to draw with complete accuracy.


0
The graph in Figure 9.8 is a straight line within our limits of 0 0.5 1.0
accuracy. It is certainly not a curve. Therefore we can conclude Concentration / mol dm–3
that the rate is proportional to the concentration of the reagent. Figure 9.8 Step 4, plotting the rate data against time. The graph
The reaction is first order with respect to that reagent. is very nearly a straight line.
Chapter 9 Chemical kinetics 95

Finding half-life
Summary
Half-life is constant for a first-order reaction.
The half-life is the time it takes for half the reagent to be ✓ The rate of a reaction can be measured in units
removed. of mol s−1 of a reagent.

Simple inspection of the data in Worked example 9.2 ✓ Most reactions occur when particles collide.
shows that the half-life is 20 seconds (look back at Table
✓ Collision frequency is altered by concentration
9.1 and look at the data for t = 20 s and t = 40 s). If the data
and temperature.
is less accommodating, then look at the graph (Figure 9.7).
Here you need to pick any two convenient concentrations ✓ Collisions must provide an activation energy
that differ by a factor of two and read off the time interval sufficient to break existing bonds.
between them. ✓ Activation energy may be lowered by a catalyst.
The mathematical rule for a first-order reaction is that
✓ Some reactions are triggered by energy input
rate = k [A] from visible or UV light.
and the half-life is given by the expression ✓ Enzymes are highly efficient biological catalysts.
0.693
t 12 = k
✓ The general rate equation is
At this stage you need not know how the expression is rate = k [A]a [B]b … [N]n.
derived. ✓ The order of a reaction is given by the sum
(a + b + … n).

Review questions
1 The following data were obtained for the reaction
A+B→P
Initial rate of
Initial [A] Initial [B]
Experiment formation of
/ mol dm–3 / mol dm–3
P / mol dm–3 s–1
1 0.10 0.10 4.0 × 10–6
2 0.20 0.10 16.0 × 10–6
3 0.20 0.20 32.0 × 10–6
4 0.40 0.20 ?

Use this data to determine:


(a) The order of the reaction with respect to reactant A.
(b) The order of the reaction with respect to reactant B.
(c) The overall order of the reaction.
(d) The rate equation for the reaction.
(e) The rate constant for the reaction.
ITQ 7 The reaction between carbon monoxide and nitrogen (f) The initial rate of formation of P for experiment 4.
dioxide is a first-order reaction with respect to carbon monoxide.
CO + NO2 → CO2 + NO
In an experiment using this reaction, NO2 was continually added
to the reaction mixture to keep its concentration in the reaction
vessel constant. It was found that the concentration of CO fell
from its initial value to half that value in 3.5 seconds.
(a) What is the value of k in the rate equation:
−d[CO]
= k[CO]
dt
(b) What are the units of k?
96 Unit 1 Module 2 Kinetics and equilibria

2 Consider the following reaction and its associated rate 6 Use the following diagram to answer the questions
law: below.
A+B→C rate = k[A]2 D

Potential energy
B
Discuss the effect that you would expect on the rate of
the reaction of each of the following changes: A
(a) Increasing the concentration of A. C
(b) Increasing the concentration of B.
(c) Increasing the temperature of the reaction.
3 The proposed mechanism for a reaction is
Reaction progress
A + B + C → D (fast)
(a) Indicate which letter represents each of the
D → E + C (slow) following:
Write: (i) the activation energy of the forward reaction
(a) the rate equation for this reaction; (ii) the heat of reaction
(b) the overall equation for the reaction. (iii) the activation energy of the reverse reaction?
(b) Is the reaction exothermic or endothermic?
4 Consider the reaction:
Explain your answer.
2H2(g) + 2NO(g) → 2H2O(g) + N2(g)
7 A large piece of calcium carbonate is reacted with
The rate law is rate = k [H2] [NO]2. At 700 °C, the dilute hydrochloric acid at a constant temperature.
rate of the reaction is 3 × 10–3 mol dm–3 s–1 when the Explain how grinding the mass of calcium carbonate
concentration of hydrogen is 1 × 10–3 mol dm–3 and into smaller particles would affect the rate of the
that of NO is 6 × 10–3 mol dm–3. reaction.
Determine: 8 Give an example of an enzyme that is very important
(a) the rate constant for the reaction; in the human body and explain its role in the body.
(b) the order of the reaction.
9 Grain that is stored in a grain elevator is unreactive.
5 At room temperature, hydrogen peroxide decomposes However, if a spark is placed near fine dust in the
to produce oxygen and water. silos, an explosive reaction will occur. Explain this
(a) Write a balanced equation to represent this observation.
reaction.
10 Use the collision theory and suitable diagrams to
(b) Suggest an experimental method that one could
explain how the following affect reaction rates:
use to determine the rate of this reaction.
(a) surface area
(c) What effect would adding manganese(IV) oxide
(b) temperature
have on the rate of this reaction?
(c) concentration
(d) Catalase, an enzyme found in liver, can cause
(d) catalyst
a change in the decomposition of hydrogen
peroxide. What effect would you expect if a piece
of liver was placed in hydrogen peroxide solution?
Chapter 9 Chemical kinetics 97

11 The following graph represents the concentration Answers to ITQs


of H2O2(aq) over time for the decomposition of
1 There would be no reaction.
hydrogen peroxide into water.
2 Inorganic reaction are often between ions which are
2H2O2(l) → 2H2O(l) + O2(g)
spherical or nearly so. Organic reactions are often
between molecules with complex shapes.
3 Pressure.
[H2O2 ] / mol dm–3

A 4 rate = k [(CH3)3CBr] [H2O]
5 They are the same.
6 mol L−1 or mol dm−3; mol dm−3 s−1
B
7 (a) Half-life is 3.5 s

Time, s
0.693
k= t 12 = 0.190
(a) Explain how the rate of reaction at A can be
constant
determined. (b) Units are = s−1
time
(b) How would you expect the rate of the reaction at
A to compare with that at B?
(c) On the same graph, sketch the general shape of a Answers to Review questions
curve, showing the concentration of H2O versus 2 (a) rate should increase
time. (b) no change since rate independent of [B]
12 In an experiment, a large excess of zinc was added to (c) increase in rate
100 cm3 of 0.2 M hydrochloric acid to produce 3 (a) rate = k[D]
240 cm3 of hydrogen. (b) A + B → E
(a) Determine the volume of hydrogen that would be 4 (a) 8.3 × 104 mol–2 dm6 s–1
produced by each of the following changes to the (b) third order
reaction:
5 (a) 2H2O2(l) → 2H2O(l) + O2(g)
(i) adding 100 cm3 of water to the reaction vessel;
(b) Determine the volume of oxygen gas produced.
(ii) adding an additional 10 g of zinc the reaction
Use a gas syringe, inverted measuring cylinder full
vessel;
of water, balance (to record mass lost).
(iii) adding an additional 50 cm3 of the 0.2 M HCl
(c) Increase the rate of decomposition.
to the reaction vessel.
(d) Increase the rate of decomposition.
(b) Describe the effect that each of the changes in part
(a) would have on the reaction rate. 6 (a) (i) A
(ii) C
(iii) B
(b) endothermic
11 (a) Draw a tangent to the curve at A and find the
slope of the tangent.
(b) Rate at B is less than at A.
(c) Increases with time.
98

Chapter 10
Chemical equilibrium
Learning objectives
■ Explain what is meant by ‘chemical equilibrium’.
■ State the characteristics of a chemical reaction
when it is at equilibrium.
■ Explain the meaning of the ‘equilibrium constant’.
■ State and use Le Chatelier’s principle.

Reversible reactions
Reactions take place when particles meet. As a reaction
continues, the number of reactant particles falls and so they
meet less often. As a result, the rate of the reaction falls. forward
Rate

There are no products at the start of the reaction, so only


the forward reaction can take place. As product particles reverse

are formed, the reverse reaction becomes possible. The rate


constant for the reverse reaction will be different from that
of the forward reaction. The reverse reaction, however slow Time

or fast, will accelerate as time goes on as the concentration Figure 10.2 Progress of a reaction: rates of forward and reverse
of the products increases (Figure 10.1). See Chapter 9 for reactions.
more about rates of reaction.
This is dynamic equilibrium because both reactions are
continuing. Neither reaction has stopped. By contrast,
products
your book is in static equilibrium on your desk: neither
the book nor the desk is moving.
Concentration

Let’s consider a general reaction:


A+BҡC+D
reactants ■ For the forward reaction:
rate = k1 [A] [B]
Time
■ For the reverse reaction:
Figure 10.1 Progress of a reaction: reagent concentration. rate = k2 [C] [D]
Sooner or later, the forward reaction and the reverse At equilibrium the rates are equal:
reaction will proceed at the same rate (Figure 10.2). This
rate = k1 [A] [B] = rate = k2 [C] [D]
means that products are formed at the same rate as they
are lost. At this point the reaction is said to be in dynamic Re-arranging this means we get:
equilibrium. The characteristic of dynamic equilibrium is k1 [C] [D]
=
that the reaction appears to stop. k2 [A] [B]
Chapter 10 Chemical equilibrium 99

Because k1 and k2 are both constants, this becomes


The expression contains p(NH3)2 and not p(NH3) because
[C] [D] there are two molecules of ammonia in the equation.
K=
[A] [B] The equation could have been written as
where K is the equilibrium constant for the reaction. N2(g) + H2(g) + H2(g) + H2(g) ҡ NH3(g) + NH3(g)
■ If K is defined in terms of concentrations of substances Similarly the partial pressure of the hydrogen appears
we refer to Kc. as p(H2)3.
■ If K is defined in terms of the pressures of gases in a
mixture we refer to Kp.
It is customary to put the concentrations of the products as Worked example 10.1
In a reaction between ethyl alcohol (EtOH) and ethanoic acid
the numerator of the ratio (the terms on top; [C] and [D]
in our example) and the concentrations of the reactants as
Q (HAc), the products are ethyl ethanoate (EtAc) and water:
the denominator (the terms underneath; [A] and [B] in EtOH + HAc ҡ EtAc + H2O
our example). Under certain conditions a mixture of 2.0 mol EtOH and 1.0 mol
HAc reacted to give, at equilibrium, 0.80 mol of EtAc.
Here are three important points about any equilibrium
Calculate the equilibrium constant for this reaction under these
constant: conditions.
■ it is only constant at a given temperature – its value
If 0.80 mol EtAc were produced then 0.80 mol EtOH and 0.80
will be different at any other temperature; A mol HAc were used.
■ it is unaffected by the presence of a catalyst – the
The remaining quantities of each are therefore:
catalyst will shorten the time needed to reach
(2.0 − 0.8) = 1.2 mol EtOH
equilibrium, but does not affect its position;
(1.0 − 0.8) = 0.2 mol HAc
■ it is determined as the ratio of two rates – if the
The equilibrium constant is given by:
forward reaction is fast compared to the reverse
[EtAc] [H2O]
reaction, the equilibrium constant will be small, and Kc =
[EtOH] [HAc]
vice versa.
If the volume of the mixture is V cm3 then we may write:
Gas reactions
Kc =
(
EtAc × 1000
V )( H2O × 1000
V )
When considering gas reactions it is possible to express
concentrations exactly, as if you were dealing with a
(
EtOH × 1000
V )( HAc × 1000
V )
solution. The units would be mol dm−3. However, it is usual 1000
All the factors cancel out so the expression reduces to:
to express gas concentrations in terms of the pressure of V
each gas in a mixture. Each gas contributes its own partial 0.8 × 0.8
pressure to the total pressure. As an example, let’s look at Kc = = 2.7 to 2 sig. figs
1.2 × 0.2
the reaction between hydrogen and nitrogen to produce
Note that in this example the factors converting quantity to
ammonia: concentration all cancel out – this may not always be the case.
N2(g) + 3H2(g) ҡ 2NH3(g) Similarly the value of Kc is a pure number – again, this may not
always be the case.
We can write:
p(NH3)2
Kp =
p(N2) p(H2)3

ITQ 1 If a reaction reaches equilibrium when only a small fraction ITQ 2 Consider this reaction:
of one reactant has been used, is the equilibrium constant low or A+BҡC
high? What are the units of the equilibrium constant?
100 Unit 1 Module 2 Kinetics and equilibria

A system in dynamic equilibrium will change to diminish


Worked example 10.2
any alteration applied to it.
At a particular temperature, 1.00 mol of hydrogen and
Q 1.00 mol of iodine were allowed to react to equilibrium. If a small change is made to a system in equilibrium, the
The total pressure in the reaction vessel at equilibrium was system will alter to minimize the change.
2.00 atm. The quantity of HI present was then 1.70 mol.
Calculate the equilibrium constant for the reaction under these Applying Le Chatelier’s principle
conditions. Let’s use the reaction between nitrogen and hydrogen,
producing ammonia, as an example:
A H2 + I2 ҡ 2HI
p(HI)2 N2(g) + 3H2(g) ҡ 2NH3(g)
Kp =
p(H2) p(I2)
Amongst other things, the equilibrium point is governed by
From the equation, we find that 1.70/2 = 0.85 mol of hydrogen the rate at which hydrogen molecules collide with nitrogen
and 0.85 mol of iodine were used up, so 1.00 − 0.85 = 0.15 mol molecules. Now consider what happens if we now inject
of each was left. The total pressure was 2.00 atm.
extra hydrogen into the system, keeping the volume the
The partial pressures were therefore:
same.
H2 I2 HI
0.15 0.15 1.70 ■ The total pressure and the partial pressure of hydrogen
atm atm atm go up.
2 2 2
■ The collision rate between hydrogen and nitrogen will
Substituting into the equation for Kp gives:

( ) 2 go up.
1.70
2 ■ The rate of production of ammonia molecules will go up.
Kp =
( )( )
= 128
0.15 0.15 After a while, there will be more ammonia molecules in
×
2 2 the mixture than before.
■ The reverse reaction, producing hydrogen and nitrogen
These examples all refer to chemical changes. But the
concept of dynamic equilibrium can be applied more widely. accelerates.
■ A new equilibrium is established.
■ A liquid in a closed container will evaporate until the
space above it is saturated with vapour. When the Nothing in that argument tells us whether the concentration
vapour is saturated the rate at which molecules leave of ammonia will go up or down. However, Le Chatelier’s
the surface is equal to the rate at which they re-enter. principle demands that the original change (the increase
in pressure caused by the addition of hydrogen) must be
■ If the rate at which water runs into a bath is equal to
minimized. To do this, the total number of molecules in the
the rate at which it runs out, the level of water in the
reaction must be reduced.
bath will not change.
■ If at a road junction, vehicles arrive at the same rate as The total number of molecules in the reaction will fall
they leave, there will be no traffic jam. If more vehicles when a molecule of nitrogen reacts completely with three
arrive per second than leave, traffic will build up at the molecules of hydrogen: four molecules in total are lost and
junction. only two molecules of ammonia are produced. So, the new
equilibrium must be one containing more ammonia than
The characteristic of a dynamic equilibrium is that the the original.
system appears to stop changing: the composition of the
mixture does not change with time.
ITQ 3
(a) State Le Chatelier’s principle.
Le Chatelier’s principle (b) State two factors that can disturb the equilibrium of a system.
(c) The equation for the calcination (decomposition) of limestone
Henry Louis Le Chatelier, a French chemist (1850–1936), can be represented as:
investigated the effect of small changes of concentration, CaCO3(s) ҡ CaO(s) + CO2(g)
pressure and temperature on systems in equilibrium. His Applying Le Chatelier’s principle, state the effect on the
result (sometimes ennobled as a ‘law’) can be stated in equilibrium when:
many ways. Because it can be difficult to understand, here i) a small quantity of CaCO3(s) is added.
are two. ii) some CO2(g) is removed.
Chapter 10 Chemical equilibrium 101

The common-ion effect The converse is true for an endothermic reaction.


A second example of how to apply Le Chatelier’s principle Equilibrium constants for gas reactions (Kp) do not change
is in the ‘common-ion effect’. The common-ion effect is with pressure if the total number of molecules is the same
when the concentration of an ion, already existing as part on both sides of the equation.
of an equilibrium mixture, is increased. For example:
A solution of copper sulfate in pure water is often slightly H2(g) + Cl2(g) ҡ 2HCl(g)
cloudy because of the reaction
[HCl]2
Cu2+(aq) + 2H2O(l) ҡ Cu(OH)2(s) + 2H+(aq) Kc =
[H2] [Cl2]
If an amount of a strong acid is added, the solution clears. However, in the Haber process reaction, shown earlier:
The concentration of the H+(aq) ion has been increased.
Le Chatelier’s principle tells us that the increase must be N2(g) + 3H2(g) ҡ 2NH3(g)
minimized. This can only happen if the reaction proceeds If the pressure at equilibrium is changed then the number
in reverse, using up some of the added hydrogen ions of molecules (and hence their concentrations) will change
and so reducing their concentration. The insoluble copper to restore the original value of Kc.
hydroxide vanishes from the mixture.
Looked at from the point of view of the equilibrium
constant, the equation leads to the expression
[H+]2
Kc =
[Cu2+]

We can ignore the concentration of the water, because it


hardly changes, and the concentration of Cu(OH)2 as it is
constant.
If [H+] is increased, the ratio Kc goes up. Le Chatelier’s
principle says that it must be reduced again. This can only
happen if either [H+] goes down or [Cu2+] goes up. When
the Cu(OH)2 dissolves, both these things happen. Some H+
is removed and some copper ions pass back into solution.
There is nothing in Le Chatelier’s principle to say how
quickly any changes will take place. It is possible that
they will happen very quickly, or that they will happen so
slowly that they are un-noticeable. This is called kinetic
hindrance.

Changes in the value of K


The position of equilibrium of a reaction, and hence the
value of K, is unchanged by the addition of a catalyst. A
catalyst speeds up the rate at which equilibrium is reached
but has no effect on its position.
Equilibrium constants (Kc) vary with temperature. If a
reaction is exothermic the reaction mixture heats up. If
a mixture is at equilibrium and is heated, Le Chatelier’s
principle demands that the temperature rise be minimized
and so the reaction tends to reverse: the concentration
of products goes down and the value of K at the higher
temperature falls below its value at the lower temperature.
102 Unit 1 Module 2 Kinetics and equilibria

Review questions
Summary
1 (a) State what is meant by Le Chatelier’s principle.
✓ A system comes to equilibrium when the rates of (b) Describe how the following equilibria would be
the forward and reverse reactions become equal. affected by the proposed changes.
(i) An increase in pressure on the reaction
✓ At equilibrium, the overall reaction appears to 2SO2(g) + O2(g) ҡ 2SO3(g) ΔH = −ve
stop.
(ii) A decrease in temperature on the equilibrium
✓ The position of equilibrium can be defined using N2(g) + 3H2(g) ҡ 2NH3(g) ΔH = −ve
an ‘equilibrium constant’. (iii) An increase in pressure on the system
✓ The equilibrium constant can be in terms of H2(g) + I2(g) ҡ 2HI(g)
concentration (Kc) or, for gases, in terms of (c) Write expressions for the equilibrium constant, Kc,
partial pressures (Kp). for each of the reactions in part (b), stating units
✓ The position of equilibrium is affected by where appropriate.
variables such as pressure and temperature. (d) State how the value of Kc for each of the reactions
in part (b) is affected by:
✓ Le Chatelier’s principle states that ‘if a small (i) change in temperature
change is applied to a system in equilibrium, (ii) change in pressure
the system will change so as to minimize the (iii) the addition of a catalyst.
change’. (e) A mixture of SO2 and O2 of concentrations
✓ Studies of equilibria give no information about a mol dm−3 and b mol dm−3 respectively reach
reaction rates. equilibrium when x moles of SO2 had reacted.
Derive an expression for Kc.
2 (a) BiCl3(l) + H2O(l) ҡ BiOCl(s) + 2HCl(aq)
Given the equilibrium above, describe how
the effect of changes in concentration can be
demonstrated.
(b) When chlorine and nitrogen(II) oxide are mixed,
an endothermic reaction occurs. The reaction can
be represented by the equation:
Cl2(g) + 2NO(g) ҡ 2NOCl(g)
(i) Deduce an expression for Kp of this reaction.
(ii) Explain the effect of an increase in
temperature on the value of Kp.
(c) Explain the effect on the position of equilibrium
caused by:
(i) an increase in pressure
(ii) the use of a catalyst.
Chapter 10 Chemical equilibrium 103

3 The second step in the Contact process used for the


manufacture of sulfuric acid involves the dynamic
equilibrium represented below:
2SO2(g) + O2(g) ҡ 2SO3(g); ΔH = –98 kJ mol−1
The reaction is carried out at 420 °C under
approximately 2 atmospheres pressure and the gases
are passed over beds of vanadium(V) oxide catalyst.
Excess oxygen is used.
(a) List four characteristics of a system that is in
dynamic equilibrium.
(b) Explain what effect (if any):
(i) the vanadium(V) oxide has on the position of
equilibrium
(ii) using a temperature of 600 °C would have
on the equilibrium concentration of sulfur
trioxide
(iii) a change in pressure on the equilibrium
system
(iv) a catalyst on the equilibrium system.

Answers to ITQs
1 Low: the concentrations of products are small and the
concentrations of reactants have hardly changed.
(mol dm−3) 1
2 = = dm3 mol−1
(mol dm−3) (mol dm−3) (mol dm−3)

3 (a) Le Chatelier’s principle states that if a change in


conditions is made to a system in equilibrium,
the system moves in the direction which will
oppose the change. The system always proceeds to
re-establish equilibrium.
(b) Changes in pressure, concentration.
(c) (i) the equilibrium shifts to the right.
(ii) the equilibrium shifts to the right.
104

Chapter 11
Acid/base equilibria
Learning objectives
■ Explain what is meant by an acid and a base.
■ Explain the meaning of ‘strong’ and ‘weak’ when applied to acids and bases.
■ Calculate the pH of an acidic solution.
■ Describe the function of a pH indicator.
■ Explain what is meant by a ‘buffer solution’.
■ Calculate the pH of a specific buffer.
■ Have an understanding of the common-ion effect.
■ Use the concept of a solubility product.

What are acids and bases? Acid/base reactions


By 1889, an acid was defined as a substance that releases Dry hydrogen chloride gas has no acidic properties. For
hydrogen ions in aqueous solution. However, a hydrogen example, it has no effect on dry indicator paper. In water,
ion – which is just a proton – is so small that the electric however, hydrogen chloride reacts as an acid:
field around it is very strong. The proton interacts with HCl(g) + H2O(l) ҡ H3O+(aq) + Cl−(aq)
neighbouring water molecules to give what is called the
oxonium ion, H3O+: Here, the water is acting as a base because it accepts a
proton from the HCl. In aqueous solution it is the H3O+
H+(aq) + H2O(l) ҡ H3O+(aq) that provides the proton for reactions.
In 1923, Brönsted and Lowry proposed the definition Similarly, dry ammonia gas reacts with water:
that an acid is a substance that donates a proton to another
substance. Working from this proposition, a base is defined H2O(l) + NH3(g) ҡ NH4+(aq) + OH−(aq)
as a substance that accepts a proton from another substance. Here, the water is acting as an acid. It donates a proton to
In an acid/base reaction, a proton is exchanged between the NH3, leaving the OH− ion to react.
the two substances.
In most aqueous reactions the water is present in excess
+
acid ҡ base + H and only a little takes part in the reactions.
base + H+ ҡ acid If we add together the products from the two equations we
This means that no substance can act as an acid unless have looked at so far, as if we were reacting HCl and NH3,
there is a base to accept the proton. The equations we have we end up with:
just used do not represent real reactions because the bare HCl(g) + NH3(g) + 2H2O(l) →
proton cannot exist in solution. In an equation where we H3O+(aq) + Cl−(aq) + NH4+(aq) + OH−(aq)
would have written H+, we can now write H3O+.
The products of this equation simplify to
The acid and the base that are related in this way are called
Cl−(aq) + NH4+(aq) + 2H2O(l)
a conjugate pair.
and we see that the only reaction in this neutralization is
between H3O+ and OH− ions.
Chapter 11 Acid/base equilibria 105

For ethanoic acid, Ka = 1.8 × 10−5, showing that dissociation


A substance which, like water, can act as both an acid
is limited. We refer to acids such as ethanoic acid as weak
and as a base is called amphoteric. The hydrogensulfate
acids.
ion, HSO4−(aq), is also amphoteric; it can react with a
base to form the sulfate ion: Acids such as hydrochloric acid are 100% dissociated in
water and we refer to them as strong acids.
HSO4−(aq) + H2O(l) ҡ H3O+(aq) + SO42−(aq)
or with an acid to form sulfuric acid: ■ A strong acid has a high concentration of H3O+.
■ A weak acid has a low concentration of H3O+.
HSO4−(aq) + H3O+(aq) ҡ H2SO4(aq) + H2O(l)
Similarly:
■ A strong base has a high concentration of OH−.
Strong and weak acids and bases ■ A weak base has a low concentration of OH−.
In Chapter 10 we saw that the position of equilibrium can
be specified by an equilibrium constant. This idea can be pKa
used for acids and bases.
In many situations, we don’t use Ka itself, but a value
Water itself is only slightly ionized: known as pKa.
2H2O(l) ҡ H3O+(aq) + OH–(aq) pKa = −log10 Ka
Kw = [H3O+] [OH−]
The term [H2O]2 does not appear in the expression for Worked example 11.1
the equilibrium constant. Because water is only slightly For ethanoic acid, Ka = 1.8 × 10−5. What is the value of pKa for
ionized, its concentration is nearly constant. Q ethanoic acid?
In pure water, the concentrations of the oxonium ion pKa = −log10 Ka
[H3O+] and the hydroxyl ion [OH−] are equal. This value is A
−log10 1.8 × 10−5 = 4.74
found to be 1 × 10−7 mol dm−3.
Therefore:
[H3O+] [OH−] = 1 × 10−14 mol2 dm−6 Worked example 11.2
Oxalic acid has Ka = 6 × 10−2. What is the value of pKa for
This is called the ionic product for water. It is true for Q oxalic acid?
any aqueous solution, not just for pure water.
pKa = −log10 Ka
Acid/base equations contain the equilibrium sign (ҡ) A
rather than a reaction arrow (→) between reactants and −log10 6.0 × 10−2 = 1.22
products. The position of the equilibrium can be anywhere
from the far left to the far right. When an substance such as
pH
ethanoic acid is in aqueous solution, it dissociates:
CH3COOH(l) + H2O(l) ҡ H3O+(aq) + CH3COO−(aq) The concentration of H3O+ ions in an aqueous solution
can be talked about by a using a quantity called the pH of
If this equilibrium lies far to the left it means that the
the solution. You will have used pH on many occasions in
solution will not contain a high concentration of H3O+. If
your study of chemistry, but perhaps only in a rough and
the equilibrium lies far to the right, the concentration of
ready way. You may have used the colour changes shown
H3O+ will be high. This is expressed by using the equilibrium
by universal indicator paper to gain an idea of the pH of a
constant for the dissociation, again leaving out [H2O] as
solution. However, pH does have a precise meaning.
this remains effectively constant during the dissociation.
The constant is given the symbol Ka. The pH of a solution is the negative logarithm to base 10 of
the concentration of the H3O+ ions in the solution.
[H3O+] [CH3COO−]
Ka =
[CH3COOH] pH = −log10 [H3O+], when [H3O+] is given in mol dm−3

ITQ 1 Why is the heat of reaction between hydrochloric acid and


sodium hydroxide roughly the same as that between nitric acid ■ Although the bare proton exists as the oxonium ion in water, the symbol
and potassium hydroxide? H+ is frequently used in its place
106 Unit 1 Module 2 Kinetics and equilibria

You need to note the following about pH:


Worked example 11.4
■ Logarithms are pure numbers, so pH has no units.
What is the pH of a solution of hydrochloric acid of
■ A change of +1 unit of pH means that the ion Q concentration 0.05 mol dm−3?
concentration has gone down by a factor of 10. A
Concentration of H3O+ is 0.05 mol dm−3.
change of −1 means that the concentration has gone A
up by a factor of 10. pH = −lg 0.05 mol dm−3 = 1.3
■ The range of pH for aqueous solutions is taken as 0 to pH of the solution is 1.3.
14.
■ The pH of a neutral solution, in which [H3O+] = [OH−],
is 7. Worked example 11.5
What is the pH of a solution of sodium hydroxide of
■ [H3O+] [OH−] = 1 × 10−14 mol2 dm−6, so pH + pOH = 14 Q concentration 0.01 mol dm−3?
■ ‘log10’ is often written as lg.
The approach here is to use the ionic product for water to link
Table 11.1 shows the [H3O+], [OH−] and pH values for A [OH−] and [H3O+].
aqueous solutions, ranging from strongly acidic to strongly
alkaline. [H3O+] [OH−] = 1 × 10−14 mol2 dm−6
Table 11.1 [H3O+], [OH−] and pH values for aqueous solutions 1 × 10−14 1 × 10−14
[H3O+] = = = 1 × 10−12 mol dm−3
[OH−] 0.01
[H3O+] / mol dm−3 [OH−] / mol dm−3 pH
1 lg 1 × 10−12 = 12
10−1 pH =12
10−2
10−3
10−4
Changes in pH in acid/base titrations
10−5 An indicator is a substance which changes colour according
10−6 to its pH. Indicators can be used alone or as a mixture such
10−7 as universal indicator. Single indicators usually have only
10−8 one colour change, such as red to blue, but this can happen
10−9 either over a very small pH range or over a greater range.
10−10
The natural substance flavin, responsible for the red colour
10−11
of fruit such as plums, is red in strong acid and green in
10−12
alkali, but between the two appears purple. Notice that:
10−13
10−14 ■ indicators change colour over a range of pH;
■ indicators do not necessarily change colour at pH 7.

Table 11.2 gives information about a range of indicators.


Worked example 11.3 Table 11.2 Common acid/base indicators

What is the pH of a solution of hydrochloric acid of Indicator Colour in acid Colour in alkali pH range
Q concentration 0.10 mol dm−3 ? methyl orange red yellow-orange 3.1–4.4
screened methyl orange red green 3.1–4.4
Hydrochloric aid is a strong acid, and is completely ionized in
A solution. Concentration of H3O+ is 0.10 mol dm−3.
bromophenol blue yellow blue 3.0–4.6
litmus red blue 4.5–8.3
pH = −lg 0.10 mol dm−3 = 1
phenolphthalein colourless magenta 8.3–10
pH of the solution is 1.
The end-point of an acid/base titration is not necessarily at
pH 7. This is because the product of the reaction (the salt)
may itself be hydrolysed. For example, sodium ethanoate
(NaEt) ionizes in water:
NaEt(aq) → Na+(aq) + Et−(aq)
ITQ 2 Show that the pH of pure water is 7.0.
Chapter 11 Acid/base equilibria 107

but the ethanoate ion (Et−) reacts with water: Added OH− ions are largely removed because they combine
Et−(aq) + H2O(l) ҡ HEt(aq) (ethanoic acid) + OH−(aq) with the acid to form its salt:

and the solution is therefore alkaline. OH−(aq) + CH3COOH(aq) ҡ CH3COO−(aq) + H2O(l)

When we titrate ethanoic acid with sodium hydroxide we Added H+ ions are removed because they combine with
therefore expect the equivalence point (the ‘end-point’) to existing ethanoate ions:
be at a pH above 7. H+(aq) + CH3COO−(aq) ҡ CH3COOH(aq)
12
11 Buffer solutions in nature
10 Buffer solutions are very common in nature.
phenolphthalein
9
■ The activity within a body cell is dependent on
8
maintenance of a constant pH in the cell fluid.
7
The fluid contains a buffer system based on the
pH

6 ethanoic acid
dihydrogenphosphate ion, H2PO4−. This ion can ionize
5
further:
4
methyl orange
H2PO4−(aq) ҡ H+(aq) + HPO42−(aq)
3
2
HCl
Any extra H+ ions entering the cell are removed as
1 H2PO4− ions. Any OH− ions entering the cell react with
0 H2PO4− ions to form HPO42− ions.
0 5 10 15 20 25 30
Volume acid added / cm 3 ■ There is a similar system in blood plasma, this time using
carbonic acid, H2CO3, and its conjugate base, HCO3−:
Figure 11.1 Titration curves for the reaction of 25 cm3 sodium
hydroxide solution with ethanoic acid (a weak acid) and H2CO3(aq) ҡ H+(aq) + HCO3−(aq)
hydrochloric acid (a strong acid). All solutions are 1.0 mol dm−3.
Added OH− ions are removed by reaction with the free
Using a strong acid there is a large and sudden pH change acid (H2CO3). H+ ions are removed by reconverting
at the equivalence point: almost any of the usual indicators the HCO3− ion to H2CO3. The buffer keeps the pH at
will change colour within one drop of the equivalence around pH 7.4 (see Worked example 11.6 below).
point. ■ Amino acids contain both the weakly basic –NH2 group
With ethanoic acid, a weak acid, methyl orange would and the weakly acidic –COOH group. They can ionize
change colour long before the equivalence point is reached. as either acids or bases, depending on the surrounding
Instead, an indicator which changes colour at above pH 7 pH. Either group can function as a buffer.
is needed. Phenolphthalein would be a good choice in this These are all good applications of le Chatelier’s principle.
case.
pH of buffer solutions
Buffer solutions The pH of a buffer solution containing a weak acid (HA)
A solution that resists changes in pH when small volumes and its sodium salt (NaA) can be calculated from the
of an acid or a base is added to it is called a buffer solution. equation for Ka:
A solution containing a weak acid and its conjugate base [H3O+] [A−]
Ka =
(e.g. as the sodium salt) will act in just this way. [HA]
Look again at Figure 11.1. Half way along the ethanoic A weak acid is only slightly ionized, so we can say that all
acid titration curve, addition of further OH− ions produces the anions come from the salt, which is completely ionized.
only a small pH change, and adding H+ ions reverses the We can also say that the concentration of the acid itself is
pH equally gently. largely unchanged, since it is mostly un-ionized.

■ screened methyl orange contains an added dye (xylene cyanol) – the


ITQ 3 Use Figure 11.1 to estimate the percentage difference in
end-point is grey and easier to see than that of methyl orange itself;
the end-points of a titration of 1.0 mol dm−3 sodium hydroxide
■ for bromophenol blue it is easy to see the mid-range colour (green); solution with 1.0 mol dm−3 hydrochloric acid using (a) methyl
■ litmus is a poor indicator because its colour change is over a big range orange and (b) phenolphthalein as the indicator.
of pH;
108 Unit 1 Module 2 Kinetics and equilibria

The equation can be arranged to become: This is characteristic of an equilibrium situation; ions are
[HA] leaving the solid lattice at the same rate as they are being
[H3O+] = Ka
[A−] re-bonded to it. For silver chloride, the solubility is about
which is the same as 6 × 10−6 mol dm−3 at 10 °C.
[acid] For such sparingly soluble substances a more useful
[H3O+] = Ka
[salt] quantity is the solubility product (symbol Ksp). This is
If we now take logarithms: the product of the concentrations of the component ions in
[acid] that solvent at that temperature. For silver chloride:
log10 [H+] = log10 [Ka] + log10
[salt] AgCl(s) ҡ Ag+(aq) + Cl−(aq)
[acid] At 10 °C the solubility is 6 × 10−6 mol dm−3. This is therefore
−log10 [H+] = −log10 [Ka] – log10
[salt] the concentration of each ion at that temperature.
[salt] Ksp = [Ag+] [Cl−]
pH = pKa + log10 
[acid]
= (6 × 10−6 mol dm−3) × (6 × 10−6 mol dm−3)
= 3.6 × 10−11 mol2 dm−6
Worked example 11.6
For most compounds, the value of the solubility product
Calculate the pH of the biological phosphate buffer when the
Q concentrations of the two phosphate species are the same.
is dependent on the temperature: at 100 °C the solubility
pKa = 7.21. product for AgCl is 2 × 10−9 mol2 dm−6.
The units of solubility product depend on the number of
A pH = pKa + log10 
[salt]
ions involved. For example, zinc hydroxide dissolves to a
[acid]
tiny extent in water at 20 °C.
If [H2PO4−] = [HPO42−] then their ratio is 1 and log10 1 = 0
Zn(OH)2(s) ҡ Zn2+(aq) + 2OH−(aq)
pH = pKa which is 7.21.
In mammals, cellular fluids need to be between pH 6.9 and Ksp = [Zn2+] [OH−]2 = 1.8 × 10−14 mol3 dm−9
pH 7.4. The buffer is therefore suited to its task! Although a saturated solution is in equilibrium, the solid
substance does not appear in the equilibrium expression.
This is because the ions are dissolved whilst the substance
Worked example 11.7 itself is solid, i.e. in a different state. In these cases only the
In blood plasma, the concentration of hydrogencarbonate ions substances on the right-hand side of the equilibrium (and
Q is about 10 times that of the free acid. What is the pH of blood? hence the numerator of the equilibrium equation) are used.
pKa of carbonic acid is 6.35.

A pH = pKa + log10 
[salt] Worked example 11.8
[acid] What is the solubility, in mol dm−3, of barium sulfate at 25 °C?
[salt] Q
= 10
[acid]
The solubility product of barium sulfate is
pH = 6.35 + log10 10
A
1.10 × 10−10 mol2 dm−6 at 25 °C.
pH = 6.35 + 1.00 = 7.35 BaSO4(s) ҡ Ba2+(aq) + SO42−(aq)
[Ba2+(aq)] = [SO42−(aq)]
Ksp = [Ba2+] [SO42−] = 1.10 × 10−10 mol2 dm−6
Solubility product
[Ba2+(aq)] = [SO42−(aq)] = 1.10 × 10−10 = 1.05 × 10−5 mol dm−3
The solubility of a material in water is commonly expressed
in mol dm−3. Sodium chloride, for example, has a solubility
in water at 30 °C of about 19 mol dm−3.
ITQ 4 Calculate the pH of a buffer solution containing 4.0 g
When a partially soluble material such as silver chloride is benzoic acid C6H5COOH and 5.0 g sodium benzoate
C6H5COONa in 1.0 dm−3 of solution.
placed in water, it slowly dissolves and the concentration
of dissolved silver ions and chloride ions rises. Ultimately, Ka benzoic acid = 6.3 × 10−5 mol dm−3
if sufficient solid is present, the dissolving appears to stop. Hint: sodium benzoate is fully ionized in solution.
Chapter 11 Acid/base equilibria 109

For calcium:
Worked example 11.9
Ksp = [Ca2+] [OH−]2 = 5.5 × 10−6 mol3 dm−9
Plants such as banana and hibiscus do not thrive in soils where
Q the pH is much above 7. This is in part because they demand a 5.5 × 10−6
[Ca2+] = = 5.5 mol dm−3
good supply of the ion Fe2+(aq). (1.0 × 10−3)2
The ionic product for water = 1.0 × 10–14 mol2 dm–6
A precipitate of calcium hydroxide will only form if
If the solubility product for Fe(OH)2 is 2 × 10–14 mol3 dm–9,
the concentration of the calcium solution is above 5.5
what is the maximum concentration of Fe2+(aq) ions in the soil
at (a) pH 7 and (b) pH 8? mol dm−3, which is unlikely to be the case with normal
laboratory solutions.
(a) at pH 7: [H+] = [OH–] = 1 × 10–7
A For magnesium:
solubility product = [Fe2+] [OH–]2 = 2 × 10–14 mol3 dm–9
2 × 10−14 Ksp = [Mg2+] [OH−]2 = 1.1 × 10−11 mol3 dm−9
[Fe2+] = = 2 mol dm–3
(1 × 10−7)2 1.1 × 10−11
[Mg2+] = = 1.1 × 10−5 mol dm−3
This is plenty for the needs of the plant. (1.0 × 10−3)2
(b) at pH 8: [H+] = 1 × 10–8 mol dm–3 A precipitate of magnesium hydroxide will form if
so [OH–] = 1 × 10–6 mol dm–3
the concentration of the magnesium solution is above
2 × 10−14 1.1 × 10−5 mol dm−3.
[Fe2+] = = 2 × 10–2 mol dm–3
(1 × 10−6)2
This is insufficient for the needs of this type of plant. Common-ion effect
In any solution the value of the solubility product for any
Testing for metal cations one solute cannot be exceeded. For example, if solid silver
chloride is put into a dilute solution of hydrochloric acid
In tests for metal cations, we often use a solution of
of concentration 0.01 mol dm−3 the solubility of the silver
ammonium hydroxide. Laboratory reagents are commonly
chloride is changed.
made to a concentration of 0.1 mol dm−3, but ammonium
hydroxide is a weak base and so is only partially ionized. The maximum value for the product [Ag+]  [Cl−] cannot
It is diluted further because we only add a few drops exceed 3.6 × 10−11 mol2 dm−6.
to the test, so the actual concentration of OH− ions is Ksp = [Ag+] [Cl−] = 3.6 × 10−11 mol2 dm−6
much reduced. Its value concentration may be around
[Cl−] = 1.0 × 10−2 (from the acid)
1.0 × 10−3 mol dm−3.
3.6 × 10−11
The metal cation solutions we are testing are often made [Ag+] = = 3.6 × 10−9 mol dm−3
1.0 × 10−2
up at about 1.0 mol dm−3.
Above this concentration the silver ions will form a
■ Calcium ions don’t form a precipitate with ammonium
precipitate.
hydroxide.
■ Magnesium ions do form a precipitate with In the absence of the acid, the concentration of Ag+ at
ammonium hydroxide. equilibrium is 6.0 × 10−6 mol dm−3.
■ The solubility product for magnesium hydroxide is The hydrochloric acid has reduced the solubility of the
−11 3 −9
1.1 × 10 mol dm . silver chloride through the common-ion effect.
■ The solubility product for calcium hydroxide is
5.5 × 10−6 mol3 dm−9.
■ The concentration of OH− in the test solution is
1.0 × 10−3 mol dm−3.
Explain why magnesium ions give a precipitate with
ammonium hydroxide but calcium ions don’t.
110 Unit 1 Module 2 Kinetics and equilibria

Review questions
Summary
1 (a) Explain what is meant by an acid and a base.
✓ An acid is a substance that donates a proton to (b) Define the pH of a solution.
another substance. (c) In pure water, the concentration of H3O+ ions is
1 × 10–7 mol dm–3. Calculate the pH of pure water.
✓ In aqueous solution, hydrogen ions (protons) (d) The dissociation constant for ethanoic acid,
form the oxonium ion H3O+.
CH3COOH, is 1.8 × 10−5 whilst that for
✓ Strong acids and strong bases are substantially 1-chloroethanoic acid is 1.4 × 10–3. Explain which
ionized in solution. is the stronger acid and calculate the pH of a
solution of that acid with a concentration of 1.0
✓ Weak acids and weak bases are only slightly
mol dm–3.
ionized in solution.
2 Note that you need to understand the idea of a
✓ The pH of a solution is the logarithm to base 10 logarithm to attempt this question.
of the H+ concentration, with the sign changed
(a) Define a ‘buffer solution’.
(usually from minus to plus).
(b) Show that for a buffer solution containing a weak
✓ pH indicators are substances which change acid and its sodium salt, the pH of the solution is
colour according to the pH of their solution. given by
[salt]
✓ The scale of pH for aqueous solutions runs from pH = pKa + log
[acid]
.
0 to 14; the neutral point is pH 7. [H+][A−]
Start from the statement that Ka = .
✓ In an aqueous solution, the product [H+] [OH−] is [HA]
always 1 × 10−14. (c) Calculate the pH of a buffer solution containing
3.0 mol dm–3 ethanoic acid and 2.0 mol dm–3
✓ A buffer solution is one that resists changes in
sodium ethanoate. (Ka for ethanoic acid is
pH.
1.8 × 10–5)
✓ The solubility product of a substance is the 3 (a) What is meant by the ‘solubility product’ of a
product of the concentrations of its cations and
compound?
anions in a saturated solution.
The usual test for the iodide ion is to add a
✓ The solubility product can be used to predict solution of lead nitrate to the test solution. A
whether a substance will be precipitated from a yellow precipitate indicates the presence of I– ions.
solution by the addition of a common ion. (b) Ksp for lead iodide, PbI2, is given in tables as
9.8 × 10–9. What are the units of this number?
(c) What is the concentration of iodide ions in a
saturated solution of lead iodide?

Answers to ITQs
1 Both are reactions between H+ and OH− ions. Other
ions take no part in the neutralization.
2 If [H3O+] [OH−] = 1 × 10−14 mol2 dm−6 and [H3O+] =
[OH−] for pure water, then [H+] = 1 × 10−7.
pH = −log10 [H+] = 7.0 (to 2 sig. figs)
3 The true end-point is when 25.0 cm3 of acid is added.
This is the result gained with phenolphthalein. Using
methyl orange, the end-point appears to be when
24.0 cm3 of acid is added.
25 − 24
The difference is therefore × 100 = 4%
25
Chapter 11 Acid/base equilibria 111

4 Molecular mass for sodium benzoate = 144 g mol−1


Molecular mass for benzoic acid = 122 g mol−1
5
Concentration of sodium benzoate = mol dm−3 = 0.035 mol dm−3
144
4
Concentration of benzoic acid is mol dm−3 = 0.033 mol dm−3
122
[H+] = 0.033 mol dm−3
Sodium benzoate is fully ionized, so [A−] = 0.035
[acid]
[H3O+] = Ka
[salt]
[0.033]
[H3O+] = 6.3 × 10−5 = 5.94 × 10−5 mol dm−3
[0.035]
pH = −log10 [H3O]+ = 4.22

Answers to Review questions


1 (c) pH = –log10 [H+]
if [H+] = 1 × 10–7 then –log10 [H+] = –7; pH = 7.0.
However, the data had only 1 significant figure, so
the final answer is: pH = 7.
(d) 1-chloroethanoic acid is the stronger acid.
[H+][CH2ClCOO−]
Ka = = 1.4 × 10−3
[CH3COOH]
The dissociation is tiny so [CH3COOH] is virtually
1.0 in this solution; also [H+] = [CH2ClCOO–]
Substituting into the expression for Ka gives
[H+]2
1.4 × 10−3 = ; [H+] = 3.7 × 10−2
1
pH = –log10 [H+] = –log10 (3.7 × 10–2)
pH = 1.43
[salt]
2 (c) pH = pKa + log10
[acid]
= –log10 (1.8 × 10–5 ) + log10 (3/2)
= 4.74 + 0.18
pH = 4.92
3 (c) Pb2+(aq) + 2I–(aq) → PbI2(s)
Ksp for lead iodide is 9.8 × 10–9 = [Pb2+][I–]2 mol3 dm–9
1
In the solution [Pb2+(aq)] = 2 [I–(aq)]
1
2 × [I–] × [I–]2 = 9.8 × 10–9
[I–]3 = 2 × 9.8 × 10–9, [I–] = 2.70 × 10–3 mol dm–3
112

Chapter 12
Redox equilibria
Learning objectives
■ Understand the reactions that take place in an electrochemical cell.
■ Describe the standard hydrogen electrode.
■ Describe methods used to measure standard electrode potentials.
■ Calculate standard cell potentials from standard electrode potentials.
■ Use standard electrode potentials to determine electron flow direction and feasibility of reaction.
■ Predict how the value of an electrode potential varies with concentration.
■ Apply the principles of redox processes to energy storage devices.

Introduction
The term ‘redox’ is an abbreviation for a process in which Redox reactions play an important role in chemistry. Their
reduction and oxidation occur simultaneously. Redox importance lies in the fact that the transfer of electrons
reactions are common in nature, in industry and everyday between species forms the basis for the functioning of
processes. For example, photosynthesis, respiration, the several devices we use in everyday life. However, in the
bleaching of hair and the rusting of iron all involve redox laboratory, devices known as electrochemical cells
reactions. can be used as vessels to carry out redox reactions. An
electrochemical cell is an apparatus which is used either for
The most useful definition of oxidation and reduction is
generating electrical energy from redox reactions, or uses
given in terms of electron transfer:
electrical energy to propel redox reactions.
■ oxidation – a reaction in which there is loss of
An electrochemical cell that spontaneously produces a
electron(s);
current is called a galvanic cell or a voltaic cell. Such a
■ reduction – a reaction in which there is gain of
cell consists of an electrical conductor (e.g. a metal strip),
electron(s).
which is called an electrode, dipping into an electrolyte,
You can remember this by using the memory aid ‘OIL RIG’: which can be either a molten ionic compound, an aqueous
■ OIL – Oxidation Is Loss solution of an ionic compound or a polar covalent
■ RIG – Reduction Is Gain compound which dissolves in water to produce ions.
The electrons lost from one reagent in an oxidation must Electrolytes conduct electricity due to the presence of
be gained by another reagent in a reduction. Oxidation and mobile or ‘free’ ions. When electrolytes conduct an electric
reduction happen together. current, the positive and negative ions, which are free to
move independently, move in opposite directions. The
■ The substance that is oxidized is called the reducing
loss or gain of electrons in the formation of ions or atoms
agent.
is a process described as the discharge of ions, and such
■ The substance that is reduced is called the oxidizing
reactions take place at the electrodes. Equations can be
agent.
written to represent these reactions taking place at each
electrode.
Chapter 12 Redox equilibria 113

Electrode potential potential difference

M
When a metal is in contact with a solution of its ions, metal
atoms tend to lose electrons (they are oxidized) and pass
into solution as aqueous ions:
M(s) → Mn+(aq) + ne− M+
e– –

– + M+
Conversely, the aqueous ions in solution may gain these e M

electrons (they are reduced) and re-form the metal: positive metal ions M+ e–
M+
M + –
Mn+(aq) + ne− → M(s) e–
negative ions – M+
In the reaction, a redox equilibrium is established when M+ –

the rate at which electrons are leaving the surface of the


metal is exactly equal to the rate at which they are being Figure 12.1 A metal in contact with a solution of its ions and the
discharged on it again. The equation for the redox reaction generation of a potential difference.
at equilibrium is written with a reversible arrow: ■ the relative reactivity of the metal;

M n+(aq) + ne− ҡ M(s) ■ the concentration of the ions in solution at equilibrium.

Reactive metals form ions readily. A less reactive metal, such as copper, does not form ions as
readily and so the equilibrium
Less reactive metals do not form ions readily.
Cu2+(aq) + 2e− ҡ Cu(s)
The ease with which a metal loses electrons is referred to as
its ‘reactivity’. For example, if a strip of the fairly reactive lies much further to the right.
zinc metal is placed in a solution of its ions, the zinc metal Thus, there is a greater tendency for the Cu2+ ions in
loses electrons readily (is oxidized) to form Zn2+ ions: solution to accept electrons from the Cu metal to re-form
Zn(s) → Zn2+(aq) + 2e− Cu atoms. The metal develops a positive charge, giving it a
positive potential.
The electrons stay on the surface of the metal, which
acquires a negative charge. The absolute potential of a single electrode cannot be
measured in isolation. How we do measure electrode
Also, some of the Zn2+ ions in solution accept these
potential will be discussed later.
electrons from the surface of the metal and are discharged
as Zn atoms:
Galvanic cells: using redox reactions to
Zn2+(aq) + 2e− → Zn(s) generate electricity
We can combine these two half-reactions:
We have established that redox reactions involve the
Zn2+(aq) + 2e− ҡ Zn(s) transfer of electrons from one species to another. This
Electrons are, by convention, written on the left-hand side transfer of electrons may be viewed as ‘a flow of electric
of the redox equilibrium. charge’, which is in fact an electric current. Therefore,
it stands to reason that redox reactions can be used to
Zinc is a fairly reactive metal. It loses electrons readily and
generate electric currents, and that such electric currents
the equilibrium lies well to the left. Many electrons are
could be used to do electrical work.
released and they stay on the metal; the metal acquires
a considerable negative charge. The solution in contact Look at an example of a galvanic cell that can be set up in the
with the zinc becomes positively charged since extra Zn2+ laboratory (Figure 12.2). In this electrochemical cell, a solid
ions have been released into it. This charge difference that Zn strip is placed into a zinc solution to form a half-cell.
develops between the negatively charged zinc strip and Similarly, a solid Cu strip is placed into a copper solution
the positively charged zinc solution is called a potential to form a second half-cell. The reactions that occur in each
difference; the zinc strip is said to have a negative half-cell are called half-cell reactions. The equations are
potential (Figure 12.1). A potential difference develops shown in Figure 12.2. These two half-cells are connected
when a metal is placed in contact with a solution of its ions. by attaching a wire from the Zn strip through a voltmeter
The sign and size of this electrode potential depends on: (which measures voltage) to the Cu strip. Once this circuit is
complete, there is a flow of electrons between the half-cells.
114 Unit 1 Module 2 Kinetics and equilibria

1.10 V ■ the K+ or Na+ ions flow to the reduction half-cell to


e– NO3

K+ e– offset the accumulation of negative charge at the
cathode.
KNO3, KCl and NaCl are suitable salts for use in a salt
bridge because:
Zn Cu
electrode electrode ■ they are soluble in water;
■ they do not react with other ions commonly used in
Zn(s) Zn2+(aq) + 2e– Cu 2+(aq) + 2e– Cu(s) electrochemical cells.
oxidation reduction
With the charge difference balanced, electrons can flow
Figure 12.2 A galvanic cell. once again, and the redox reactions can proceed.
We know that like charges repel. Therefore, it stands to
The anode, which is the more negative electrode,
reason that since electrons are negatively charged, electrons
is conventionally placed on the left when drawing
will tend to flow away from the negative electrode and
diagrams of these cells.
towards the positive electrode in an electrochemical cell. As
a result, the following occurs: ■ The anode is negatively charged since the
spontaneous oxidation at the anode is the source of
■ electrons flow out of the left-hand half-cell through
the cell’s electrons or negative charge.
the Zn strip (labelled with a negative sign); this strip
■ The cathode is positively charged.
is called the anode and since electrons are lost here,
oxidation occurs at the anode
Electrical voltage is a measure of the tendency of electrons
■ electrons flow into the right-hand half-cell through the to flow:
Cu metal strip (labelled with a positive sign); this strip
V = IR (voltage = current × resistance)
is called the cathode and since electrons are gained
here, reduction occurs at the cathode. A flow of electrons in the external circuit indicates a
As electrons flow out of the oxidation half-cell through difference in potential between the two electrodes; this
the Zn strip, Zn2+ ions form in this cell. These electrons difference in potential is called an electromotive force,
then pass through the wire into the reduction half-cell e.m.f. or E (if measured under standard conditions)
via the Cu strip. The Cu2+ ions in the reduction half-cell and is measured in volts. The e.m.f. is determined using
are deposited as neutral Cu atoms. As electrons leave one a high-resistance voltmeter which uses negligible current
half-cell and flow to the other, a difference in charge is in the external circuit, and therefore the cell registers its
established. Normally, this charge difference would prevent maximum potential difference. The e.m.f. of the zinc/
further flow of electrons. However, a device known as a copper cell is 1.10 V.
salt bridge addresses this problem. This device is often an
inverted U-shaped tube and contains a strong electrolyte The standard hydrogen electrode (S.H.E.)
such as KNO3, KCl or NaCl. The electrolyte is often jellified
We pointed out earlier that the absolute potential of a single
with agar to help prevent intermixing of fluids.
electrode cannot be measured in isolation. E.m.f.s can only
Note that ions pass through the salt bridge but electrons be measured for a complete circuit with two electrodes. In
flow through the wire. other words, only differences in potentials are measurable.
The salt bridge serves the following functions: However, it would be useful if we could in fact assign a
characteristic electrode potential value to half-cells. To
■ it joins the two half-cells and allows the flow of ions to
achieve this, electrode potentials are measured relative
maintain a balance in charge between these cells; to the standard hydrogen electrode, S.H.E., which is
■ it keeps the contents of each cell separate; assigned a potential of 0.00 V (Figure 12.3). The half-cell
■ the NO3− or Cl− ions within the salt bridge flow to under test is connected to the S.H.E. and the potential
the oxidation half-cell to offset the accumulation difference of the cell is measured; this difference is called
of positive charge at the anode and hence maintain the standard electrode potential, E of the cell.
electrical neutrality;
ITQ 1 Why do electrons flow through the voltmeter from left to
right in Figure 12.2?
Chapter 12 Redox equilibria 115

high-resistance voltmeter
V

hydrogen in
H2(g) at 298 K at 1 bar
salt bridge
and 1 atm pressure

acid solution
containing
1.0 mol dm–3
H+(aq)

glass tube with holes


platinum in to allow bubbles of
electrode H2(g) to escape S.H.E. half-cell under test

Figure 12.3 The standard hydrogen electrode (S.H.E.). Figure 12.4 Measuring the standard electrode potential of a
half-cell.

The S.H.E. consists of hydrogen gas bubbling around a The potential of the half-cell under test is equal to the
platinum electrode immersed in a solution of H+ ions under e.m.f. of the cell.
standard conditions. Hydrogen is adsorbed on the platinum If, however, the S.H.E. forms the positive electrode in the
and an equilibrium is established between the adsorbed cell, then:
layer of H2 gas and H+(aq) ions in the solution:
E = E(positive electrode) − E(negative electrode)
2H+(aq) + 2e− ҡ H2(g) E = 0.00 V
= 0.00 − E(negative electrode)
The platinum electrode is ‘platinized’, which means that
it is coated with a layer of finely divided platinum. This = −E(positive electrode)
serves to increase its surface area so that the equilibrium In this case, the potential of the half-cell under test is
between the H2(g) and H+(aq) can be established as quickly numerically equal to the e.m.f. of the cell, but has a
as possible. negative value.
The platinum electrode has two important properties: For example, the standard electrode potential of the
■ it is inert and does not form platinum ions; Cu2+(aq)/Cu(s) half-cell is measured by connecting it to
the S.H.E., as shown in Figure 12.4. The standard electrode
■ H2 gas is readily adsorbed onto its surface.
potential of the Cu2+(aq)/Cu(s) half-cell is thus the potential
Standard conditions are as follows: difference between the electrodes of a cell consisting of the
■ temperature of 25 °C (298 K); S.H.E. and the standard Cu2+(aq)/Cu(s) half-cell.
■ gases at 1 atm pressure (101.3 kPa ,1 bar) In this cell:
■ 1.00 mol dm−3 solutions.
■ the reactions occurring at the electrodes are:
H2(g) + 2e− ҡ 2H+(aq)
Measuring standard electrode potentials
Cu2+(aq) + 2e− ҡ Cu(s)
The standard electrode potential, E , of a standard half-cell
■ electrons flow from the S.H.E. to the Cu2+(aq)/Cu(s)
is the potential of that half-cell relative to the S.H.E. under
half-cell;
standard conditions. The e.m.f. of an electrochemical cell
■ the Cu electrode is positive;
is given by:
■ the S.H.E. is negative;
E = E(positive electrode) − E(negative electrode)
■ the e.m.f. is 0.34 V.
The ‘minus’ sign is because we regard the two half-cells as Remember: electrons flow away from the negative
working against one another. electrode and towards the positive electrode.
If the S.H.E. forms the negative electrode in the cell, then: Since the Cu electrode is positive, the standard electrode
E = E(positive electrode) − E(negative electrode) potential for the Cu2+(aq)/Cu(s) half-cell is +0.34 V. This is
= E(positive electrode) − 0.00 written as:

= E(positive electrode) Cu2+(aq) + 2e− ҡ Cu(s) E = +0.34 V


116 Unit 1 Module 2 Kinetics and equilibria

Now consider what happens when a standard zinc half-cell


is connected to the S.H.E.:
■ the reactions occurring at the electrodes are: solution containing
equal concentrations
2H+(aq) + 2e− ҡ H2(g) of Fe 2+(aq) and Fe3+(aq)

Zn(s) + 2e− ҡ Zn2+(aq)


■ electrons flow from the Zn2+(aq)/Zn(s) half-cell to the platinum
electrode
S.H.E.;
■ the Zn electrode is negative; Figure 12.5 The Fe3+(aq)/Fe2+(aq) half-cell.
■ the S.H.E. is positive; In this system:
■ the e.m.f. is 0.76 V.
■ there is no metal to allow electron transfer;
Since the Zn electrode is negative, the standard electrode ■ iron exists in two different oxidation states;
potential for the Zn2+(aq)/Zn(s) half-cell is −0.76 V. This is ■ equimolar solutions are used;
written as: ■ platinum serves as an inert electron carrier.
2+(aq) 2e− ҡ Zn(s)
Zn + E = −0.76 V Other examples:
Conventionally, the S.H.E. is placed on the left-hand side ■ the Br2(aq)/Br−(aq) half-cell is set up with a platinum
of the electrochemical cell. In this way, the sign of the electrode immersed in a solution containing
standard electrode potential of a half-cell indicates whether 1.0 mol dm−3 of Br− ions;
that electrode is positive or negative. ■ the Cl2(g)/Cl−(aq) half-cell involves a gas and so the
The hydrogen electrode is not an easy device to manipulate half-cell consists of chlorine gas bubbling over a
and in practice the calomel cell, which is based on platinum electrode immersed in a solution containing
mercury chloride, Hg2Cl2, is used as a secondary standard. 1.0 mol dm−3 of Cl− ions.
The calomel cell has E = +0.24 V.
Uses of standard electrode potentials
Measuring the E of half-cells involving Relative oxidizing and reducing powers
non-metals
Standard electrode potentials can be arranged in order of
Thus far, we have dealt only with redox reactions that their values from the most negative through to the most
involve metals. However, some redox reactions do not positive to produce a list known as the electrochemical
involve metals. Instead, non-metal ions of the same series (Table 12.1).
elements exist in different oxidation states. If a half-cell In Table 12.1, the electrode reactions are written as
doesn’t involve a metal, then remember that a platinum reduction processes, so that electrons are added on the
electrode can be used as an electron carrier. The platinum left-hand side.
electrode is immersed in a solution containing 1.0 mol
■ Li+(aq), found at the top of Table 12.1, is the strongest
dm−3 of metal ions. The standard electrode potential of
the half-cell under test is measured by connecting it to the reducing agent but is the weakest oxidizing agent. As
S.H.E. (or a secondary standard) under standard conditions. you go down the list, the oxidizing strength increases.
Figure 12.5 shows a half-cell involving a non-metal. ■ F2(g), found at the bottom of Table 12.1, is the strongest
The Fe3+(aq)/Fe2+(aq) half-cell is set up with a platinum oxidizing agent but is the weakest reducing agent. As
electrode immersed in a solution containing 1.0 mol dm−3 you go up the list, the reducing strength increases.
of Fe3+ ions and 1.0 mol dm−3 of Fe2+ ions. ■ Hydrogen is found mid-way down Table 12.1, with a
E value of 0.00 V.

ITQ 2 ITQ 3 Will iodide ions react with chlorine gas? Explain your
answer.
(a) Draw a labelled diagram to show how the E value for the
Zn2+(aq)/Zn(s) electrode can be found.
(b) Which is the positive electrode? ITQ 4 Which one of the following metals is capable of reducing
(c) Indicate the direction in which electrons flow. Sn4+ to Sn2+? Cu, Zn or Ag.
Chapter 12 Redox equilibria 117

Table 12.1 Standard electrode potentials arranged in an The data in Table 12.1 provides invaluable information on
electrochemical series redox systems.
Electrode process E /V
The data can act as a guide to the reactivity of species. The
Li+(aq) + e− ҡ Li(s) −3.03
most reactive metals are at the top of the series, whilst
Rb+(aq) + e− ҡ Rb(s) −2.93 the most reactive non-metallic species are to the bottom.
K+(aq) + e− ҡ K(s) −2.92 This makes sense. Metals always react by losing electrons,
Sr2+ (aq) + 2e ҡ Sr(s) − −2.89 and species which lose electrons most readily will have
Ca2+ (aq) + 2e ҡ Ca(s) − −2.87 large negative electrode potentials. On the other hand,
Na+ −
(aq) + e ҡ Na(s) −2.71 non-metals generally form ions by gaining electrons.
Mg2+ (aq) + 2e ҡ Mg(s)− −2.37
You need to bear in mind that individual reactions
Be2+ (aq) + 2e ҡ Be(s) − −1.85 may be kinetically hindered. Just as thermodynamic
Al3+(aq) + 3e− ҡ Al(s) −1.66 data can tell us whether a reaction is feasible but give
Mn2+ (aq) + 2e ҡ Mn(s)− −1.19 no hint about the reaction rate, the difference between
Zn2+(aq) + 2e− ҡ Zn(s) −0.76 the electrode potentials of two half-reactions can give
Cr2+(aq) + 3e− ҡ Cr(s) −0.74 information about the position of equilibrium of their
combined reaction, but tells us nothing about how
2CO2(g) + 2H+(aq) + 2e− ҡ H2C2O4(aq) −0.49
quickly that equilibrium is reached.
Fe2+(aq) + 2e− ҡ Fe(s) −0.44
Cr3+(aq) + e− ҡ Cr2+(aq) −0.41 The data can act as a measure of the oxidizing and
Ti3+ −
(aq) + e ҡ Ti (aq) 2+ −0.37 reducing powers of species. Negative E values show that
Co2+(aq) + 2e− ҡ Co(s) −0.28 the species loses electrons (i.e. it is oxidized) more readily
Ni2+(aq) + 2e− ҡ Ni(s) −0.25 than hydrogen and hence acts as a reducing agent. On the
Sn2+ (aq) + 2e ҡ Sn(s) − −0.14 contrary, positive E values show that the species gains
electrons (i.e. it is reduced) more readily than hydrogen
Pb2+(aq) + 2e− ҡ Pb(s) −0.13
1
and hence acts as an oxidizing agent.
H +(aq) + e− ҡ 2 H2(g)
0.00
Sn4+(aq) + 2e− ҡ Sn2+(aq) +0.15 Note that this does not mean that for a reaction to occur,
the E value for one half of the reaction must be positive
Cu2+(aq) + e− ҡ Cu+(aq) +0.15
and the must be other negative. All that is needed is that
Cu2+(aq) + 2e− ҡ Cu(s) +0.34
1
one value must be more negative than the other to act as
2 O2(g) + H2O(l) + 2e− ҡ 2OH−(aq) +0.40
the reducing agent, while the more positive of the two acts
+(aq) e− ҡ Cu(s) +0.52
Cu + as the oxidizing agent.
1
2 I2(aq) + e− ҡ I−(aq) +0.54
If we compare the positions of Zn and Cu in the

MnO4 (aq) + e− ҡ MnO4 (aq) 2− +0.56
electrochemical series, as well as their E values, we can
Fe3+(aq) + e− ҡ Fe2+(aq) +0.77 see that Zn is higher than Cu and has the greater negative
Ag+(aq) + e− ҡ Ag(s) +0.80 E value:
NO3−(aq) + 4H+(aq) + 3e− ҡ NO(g) + 2H2O(l) +0.96
Zn2+(aq) + 2e− → Zn(s) E = −0.76 V
1
2 Br2(g) + e− ҡ Br−(aq) +1.09 Cu2+(aq) + 2e− → Cu(s) E = +0.34 V
1 +1.19
IO3−(aq) + 6H+(aq) + 5e− ҡ 2 I2(aq) + 3H2O(l)
From these numbers, we can deduce the following:
MnO2(s) + 4H+(aq) + 2e− ҡ Mn2+(aq) + 2H2O(l) +1.23
1 2− 7 ■ Zn is more reactive than Cu;
2 Cr2O7 (aq) + 7H+(aq) ҡ Cr3+(aq) + 2 H2O(l) +1.33
1 ■ Zn is a stronger reducing agent than Cu;
2 Cl2(aq) + e− ҡ Cl−(aq) +1.36
■ Cu2+ is a stronger oxidizing agent than Zn2+.
Mn3+(aq) + e− ҡ Mn2+(aq) +1.51
MnO4−(aq) + 8H+(aq) + 5e− ҡ Mn2+(aq) + 4H2O(l) +1.51
Calculating standard cell potentials
Pb4+(aq) + 2e− ҡ Pb2+(aq) +1.69
Follow this sequence of steps in order to calculate the
Co3+(aq) + e− ҡ Co2+(aq) +1.81
standard cell potential, E cell .
S2O82−(aq) + 2e− ҡ 2SO42− (aq) +2.01
1 1 Write the two half-cell reactions and their respective
2 F2(aq) + e− ҡ F−(aq) +2.87
E values.
118 Unit 1 Module 2 Kinetics and equilibria

2 The half-cell carrying the more negative (or less


The convention of writing the anode process on the
positive) E value forms the anode. Re-write this
left-hand side in the cell diagram (Figure 12.6) leads to a
anodic reaction as an oxidation reaction, i.e. loss of
positive cell voltage. This represents the flow of electrons
electrons. Change the sign of the voltage.
from left to right in the cell.
3 Balance the loss/gain of electrons (if necessary). Note
that the E value is independent of the number of If the cell diagram were written the other way around,
electrons transferred. we would get a negative cell voltage, which indicates
that the cell reaction as written cannot take place.
4 Add the anode half-cell to the cathode half-cell.
5 When two half-cells are connected under standard The zinc/copper half-cell arrangement we have been
conditions, the resulting electrochemical cell registers studying closely resembles one of the first practical cells
its maximum potential difference or e.m.f., which is to be used – known as the Daniell cell. The Daniell cell is
called the standard cell potential, E cell . discussed in more detail later (page 120).
This standard cell potential can be calculated from the
standard electrode potentials of the half-cells. Feasibility of reactions
A reaction is feasible only if the standard cell potential is
Worked example 12.1 positive. By extension, a negative e.m.f. implies that the
Calculate the standard cell potential of the zinc/copper cell. reaction is not feasible. The standard cell potential for the
Q zinc/copper cell, as calculated above, is +1.10 V, suggesting
that the reaction is energetically feasible.
1 Write the half-cell equations and find their standard
A electrode potentials (see Table 12.1).
Zn2+(aq) + 2e− → Zn(s) E = −0.76 V Worked example 12.2
Cu2+(aq) + 2e− → Cu(s) E = +0.34 V Will a cell containing a copper electrode and a silver electrode
2 The zinc half-cell carries the more negative E value, Q be feasible? If it is, what is its standard potential?
therefore zinc is more reactive than copper and becomes Note: E values are independent of the number of electrons
the anode. We need to re-write the Zn half-cell as an transferred.
oxidation-type reaction:
Zn(s) − 2e− → Zn2+(aq) E = +0.76 V A Cu2+(aq) + 2e− → Cu(s) E = +0.34 V
Since the reaction is now written as an oxidation instead of Ag (aq) + e → Ag(s)
+ − E = +0.80 V
a reduction, the sign of the voltage becomes positive. The copper half-cell carries the less positive E value, therefore
3 The loss and gain of electrons are already equal, i.e. two copper is more reactive than silver and becomes the anode.
electrons are lost and two are gained. Re-write the Cu half-cell as an oxidation type reaction:
4 The anode half-cell is added to the cathode half-cell: Cu(s) − 2e− → Cu2+(aq) E = −0.34 V
Zn(s) − 2e− → Zn2+(aq) +0.76 V anode half-cell Since the reaction is now written as an oxidation instead of a
Cu (aq) + 2e− → Cu(s)
2+ +0.34 V cathode half-cell reduction, the sign of the voltage becomes negative.
Zn(s) + Cu (aq) → Zn (aq) + Cu(s) +1.10 V E cell
2+ 2+
Since two electrons are lost in the copper half-cell, two
The cell voltage is 1.10 V. electrons should be gained in the silver half-cell. Therefore, the
silver half-cell reaction is multiplied by two to give:
The combination of half-cells and the resulting cell e.m.f. 2Ag+(aq) + 2e− → 2Ag(s) E = +0.80 V
can be summarized in the following cell diagram (Figure The anode half-cell is added to the cathode half-cell:
12.6). Cu(s) − 2e− → Cu2+(aq) E = −0.34 V
Zn 2+(aq) Cu 2+(aq) Cu(s) E cell = 1.10 V 2Ag (aq) + 2e → 2Ag(s)
+ − E = +0.80 V
’

Zn(s)
salt
Cu(s) + 2Ag (aq) → Cu (aq) + 2Ag(s)
+ 2+ E cell = +0.46 V
anode process bridge cathode process e.m.f. The positive e.m.f. value of +0.46 V indicates that the reaction
Figure 12.6 A cell diagram. is feasible.

ITQ 5 The standard copper half-cell is connected to a standard silver half-cell. ITQ 6 Will aluminium metal displace
(a) What is the term used to describe the potential difference obtained? copper(II) ions from an aqueous solution?
(b) Which cell acts as the negative electrode? Write balanced equations for this reaction
(c) Calculate the potential difference obtained when the two half-cells are connected. and describe any changes observed.
Chapter 12 Redox equilibria 119

Kinetic feasibility It was earlier in this chapter that standard electrode


potentials were measured under standard conditions.
There are times when the calculation gives a standard cell
Therefore, if these conditions are changed, i.e. if there are
potential that is positive. However, in practice, the reaction
changes in temperature, pressure or concentration, the
may be too slow to notice. E values relate only to the
electrode potential values will also change. It is possible
relative stabilities of reactants and products, and therefore
to maintain the standard conditions of temperature and
only indicate the feasibility of a reaction from an energetic
pressure. However, maintaining the standard conditions
standpoint. E values give no information about the rate
of concentration (1.0 mol dm−3) is impossible in practice
of a reaction or its kinetic feasibility.
because as soon as a reaction begins, the concentrations of
Take, for example, the E values that predict Cu2+(aq) both the reactants and the products change.
should oxidize H2(g) to H+(aq). Let us calculate the standard
Let us look at the effect of concentration on the value of
cell potential for this redox system:
the standard electrode potential.
Cu2+(aq) + 2e− → Cu(s) E = +0.34 V
Cu2+(aq) + 2e− ҡ Cu(s) E = +0.34 V
2H+(aq) + 2e− → H2(g) E = 0.00 V
If the concentration of Cu2+(aq) decreases, then, according
The hydrogen half-cell carries the less positive E value.
to Le Chatelier’s principle, the equilibrium will shift to
We need to re-write the hydrogen half-cell as an oxidation
the left in order to restore the concentration of Cu2+(aq)
type reaction:
and release more electrons. Electrons are negatively
H2(g) − 2e− → 2H+(aq) E = 0.00 V charged and therefore when the equilibrium moves to the
The loss and gain of electrons are already equal. left the E value becomes more negative (less positive).
Consequently, the electrode potential of copper in contact
The anode half-cell is added to the cathode half-cell: with 0.10 mol dm−3 Cu2+(aq), for example, rather than the
H2(g) − 2e− → 2H+(aq) E = 0.00 V standard 1.00 mol dm−3, is reduced. The value is found to
Cu2+(aq) + 2e− → Cu(s) E = +0.34 V be 0.31 V.
H2(g) + Cu2+(aq) → 2H+(aq) + Cu(s) E cell = +0.34 V Zn2+(aq) + 2e− ҡ Zn(s) E = −0.76 V
The positive e.m.f. value of +0.34 volts indicates that If the concentration of Zn2+(aq) decreases, then, according
the reaction is theoretically feasible. However, nothing to Le Chatelier’s principle, the equilibrium will shift to
happens when hydrogen is bubbled into copper(II) sulfate. the left, as with the copper example above. The E value
In this instance, the reaction is so slow that the reaction becomes more negative. As a result, the electrode potential
rate is in effect zero. of zinc in contact with 0.10 mol dm−3 Zn2+(aq) is more
negative. The value is found to be −0.79 V.
Let us now compare the reaction below and determine if it
is energetically feasible.
Energy storage devices
Cu2+(aq) + 2Ag(s) → Cu(s) + 2Ag+(aq)
Electrochemical cells use redox reactions to generate
The e.m.f. is calculated as follows:
electrical energy; examples are batteries and cells. A
Cu2+(aq) + 2e− → Cu(s) E = +0.34 V battery consists to two or more cells connected in series
2Ag(s) − 2e− → 2Ag (aq)
+
E = −0.80 V or parallel; however; the term is sometimes used for single
Cu2+ (aq) + 2Ag(s) → Cu(s) + 2Ag (aq) E cell = −0.46 V
+ cells. Batteries and cells convert chemical energy into
electrical energy. Batteries can be of two types, primary
This reaction will not occur because the overall e.m.f. is
and secondary.
negative.
■ Primary cells produce an e.m.f. from irreversible

The effect of concentration on electrode chemical reactions. Once the chemicals are used up,
the cell cannot be restored or recharged and must be
potential
discarded.
In Chapter 10 we were introduced to Le Chatelier’s principle. ■ Secondary cells produce e.m.f. from reversible
This states that, if a change in conditions is made to a chemical reactions. The chemicals are restored by
system in equilibrium, the system moves in the direction passing an electric current through the battery in the
that will oppose the change. The system always proceeds to opposite direction of normal cell operation.
re-establish equilibrium.
120 Unit 1 Module 2 Kinetics and equilibria

cells batteries Dry-cell batteries


Dry-cell batteries are so-called because they do not contain
primary secondary large amounts of solution. They are widely used in small
electrical appliances such as flashlights, radios, bicycle
non-rechargeable rechargeable lamps and electric bells. There are several common types of
one time use can be reused dry-cell batteries. They include the Leclanché dry cell and
the alkaline battery.
Daniell cell lead-acid
accumulator Leclanché dry-cell
Leclanché cell
One of the most common, inexpensive and convenient
alkaline battery
types of dry cell is the Leclanché dry cell (Figure 12.9).
fuel cell This was invented in 1867 by Georges Leclanché, a French
electrical engineer (1839–1882).
Figure 12.7 Types of cells.
In the Leclanché dry cell the cathode (positive terminal) is a
Figure 12.7 summarizes the types of electrochemical cells
central carbon rod surrounded by a mixture of manganese
that will be discussed in this section of the chapter.
dioxide and carbon powder (usually graphite powder)
(Figure 12.9). The manganese dioxide prevents the build-
The Daniell cell
up of hydrogen gas bubbles on the terminal, which would
The Daniell cell was one of the first practical and reliable reduce its efficiency. It does this by oxidizing the hydrogen
cells to be used as a source of electricity. It was invented produced at the electrode to water. The carbon powder
in 1836 by John Frederic Daniell, an English chemist increases the surface area of the positive terminal to
(1790–1845), and closely resembles the Zn2+(aq)/Zn(s) and increase the electrical conductivity.
Cu2+(aq)/Cu(s) half-cell set-up. The only difference lies in
the way in which the ions are allowed to flow between
metal cap (+)
the two half-cells. The Daniell cell (Figure 12.8) uses a
porous pot to allow the flow of ions whilst stopping the
two solutions from mixing. The laboratory Zn2+(aq)/Zn(s)
and Cu2+(aq)/Cu(s) half-cell set-up uses a salt bridge. carbon rod
zinc case
(positive electrode)
In the Daniell cell, a central zinc anode dips into a porous (negative electrode)

pot containing zinc sulfate solution. The porous pot is moist paste of
immersed in a solution of copper sulfate contained in a ammonium chloride
(electrolyte) manganese(IV) oxide
copper can, which acts as the cell’s cathode. The Daniell
cell is a primary cell and, as we saw previously, it produces
1.10 V.
zinc rod metal bottom (–)

Figure 12.9 The Leclanché dry cell.

The next layer is the electrolyte, which consists of a paste


copper can
of ammonium chloride (as a source of H+ ions) and zinc
chloride dissolved in water. And all of this is contained
porous pot within the anode (negative terminal) which is made of zinc
copper sulfate and also serves as the outside shell of the battery.
solution
The Leclanché dry cell makes use of these two reactions:
zinc sulfate
solution at the anode: Zn(s) → Zn2+(aq) + 2e−
at the cathode: 2MnO2(s) + 2H+(aq) + 2e− →
Mn2O3(s) + H2O(l)
Figure 12.8 The Daniell cell.

ITQ 7 Suggest changes which could be made to the zinc/copper


cell to cause the e.m.f. to be greater than 1.10 V?
Chapter 12 Redox equilibria 121

The H+ ions are in turn provided by ammonium ions, NH4+, The lithium-ion cell
through the reaction: Nowadays, lithium-ion cells are more and more used,
NH4+(aq) + water → H+(aq) + NH3(aq) because they can deliver more energy per gram and can be
recharged time after time with no loss of function.
The Leclanché dry cell can be summarized as:
They are based on the half-reaction:
Zn(s) | Zn2+(aq) || 2NH4+(aq) | [2NH3(g) + H2(g)] | C(graphite)
Li+ + e− → Li E = −3.03 V
E cell = +1.5 V
The lithium-ion cell has one of the most negative electrode
When the dry cell is in use, the zinc casing becomes thinner
potentials known.
as the zinc is oxidized to zinc ions and the electrolyte oozes
out of the battery. Even when the cell is not in use, the zinc One electrode is the compound LiCoO2 and the other is
casing is eaten away since the ammonium chloride inside carbon. In the charge/discharge cycle, lithium ions move
the battery is acidic and reacts with the zinc. from the lithium/cobalt compound through a micromesh
electrode separator to the carbon cathode and back again.
A number of variants subsequently followed, and by
These batteries can be recharged without the ‘memory
1889 (22 years after its discovery), there were at least six
effect’ which limits others such as the Ni-H cell.
well-known dry batteries in use.

Alkaline battery Fuel cells


Alkaline batteries are comparable to the Leclanché dry cell. Fuel cells use fuels such as hydrogen, hydrocarbons and
As opposed to the acidic ammonium chloride/zinc chloride alcohols as a source of chemical energy and convert them
electrolyte found in the Leclanché dry cell, alkaline batteries to electrical energy. The reaction between a fuel supply
use an alkaline electrolyte of potassium hydroxide; hence and an oxidizing agent generates electricity. Fuel cells are
they acquired the name ‘alkaline battery’. primary cells but differ from conventional electrochemical
cells in that the fuel producing the electricity can be
In the alkaline battery:
constantly replenished. Therefore, fuel cells can operate
■ the cathode is made of manganese dioxide; continuously provided the necessary reactants are provided
■ the anode is made of zinc powder, which gives more continuously.
surface area for increased current.
There are many types of fuel cells, but the mode of
The half reactions are: operation and characteristic features are all the same. The
at the anode: Zn(s) + 2OH−(aq) → ZnO(s) + H2O(l) + 2e− design of all fuel cells features three compartments which
are sandwiched together: the anode, the electrolyte and
at the cathode: 2MnO2(s) + H2O(l) + 2e− →
the cathode. The electrodes are coated with a catalyst. One
Mn2O3(s) + 2OH−(aq)
of the most important is the hydrogen/oxygen fuel cell
The different electrolyte system in the alkaline battery (Figure 12.10).
accounts for the higher electrochemical efficiency as e– e–
compared to the Leclanché counterpart. This increased H2O(g)

electrochemical efficiency gives rise to its increased


capacity, longer storage life and better performance at both porous porous carbon
high and low temperatures. The nominal voltage of a fresh carbon anode cathode containing
alkaline cell is also 1.5 V. Although this voltage falls every containing Ni Ni and NiO

time it is used, the rate at which it declines is not as steep


as in the Leclanché cell. H2(g) O2(g)

oxidation: reduction:
2H2(g) + 4OH–(aq) O2(g) + 2H2O(l) + 4e–
4H2O(l) + 4e – 4OH–(aq)

ITQ 8 Why is the Leclanché dry cell more convenient and warm KOH
portable than the Daniell cell? solution

Figure 12.10 A hydrogen/oxygen fuel cell.

ITQ 9 Why is the NH4Cl/ZnCl2 electrolyte used as a paste as


opposed to a dry solid?
122 Unit 1 Module 2 Kinetics and equilibria

In this cell: Lead–acid accumulator (car battery)


■ hydrogen is the fuel; An ‘accumulator’ is a storage device. To supply electrical
■ oxygen (usually from the air) serves as the oxidizing power in motor vehicles a battery is used that is made up
agent; of either three or six secondary cells based on the reaction
■ the anode and cathode are porous graphite electrodes between lead and sulfuric acid. Each cell generates a
impregnated with either nickel or platinum catalysts; voltage of about 2 V: the battery therefore produces either
■ the electrolyte is warm potassium hydroxide solution. 6 V or 12 V. Each lead–acid cell (Figure 12.11) consists of
a lead anode and a lead(IV) oxide cathode immersed in
H2(g) enters the negative compartment and diffuses through
dilute sulfuric acid (roughly 5 mol dm–3) as the electrolyte.
the porous anode. The nickel catalyst on the anode breaks
Although these batteries are heavy and have a low charge/
down the H2(g) to H+(aq) ions and electrons. The H+(aq)
volume ratio, they can provide large currents for short
ions enter into the KOH solution where they combine with
times and as such are ideal for powering starter motors.
the OH−(aq) ions in solution to produce H2O(l) as a waste
gas vents
chemical. positive terminal
lead
The electrons flow through an external circuit to the negative terminal

cathode, creating an electrical current.


The overall reaction at the anode is:
lead oxide
2H2(g) + 4OH−(aq) → 4H2O(l) + 4e−
O2(g) enters the positive compartment and diffuses through
the porous cathode. At the cathode, the oxygen combines
sulfuric acid
with water and electrons to form hydroxide ions: insulating case

O2(g) + 2H2O(l) + 4e− → 4OH−(aq) Figure 12.11 A lead–acid battery.


The overall reaction (obtained by adding the anode and During cell operation, the lead anode dissolves to form
cathode reactions) is: lead(II) ions:
2H2(g) + O2(g) → 2H2O(l) Pb(s) → Pb2+(aq) + 2e−
As long as there is a supply of hydrogen and oxygen to At the positive terminal, the lead(IV) oxide cathode reacts
this cell, it will continue to operate and produce electrical with the H+ ions in the sulfuric acid, also forming lead(II)
energy. The potassium hydroxide is kept warm so that the ions and water:
water produced by the cell reaction evaporates just as fast
as it is formed. Otherwise, the water will gradually dilute PbO2(s) + 4H+(aq) + 2e− → Pb2+(aq) + 2H2O(l)
the potassium hydroxide, rendering the cell inoperative. The Pb2+ ions formed at the electrodes react with SO42−
Fuel cells have a significant advantage over all other ions in the acid to form insoluble lead(II) sulfate:
devices that convert chemical energy to electrical energy: Pb2+(aq) + SO42−(aq) → PbSO4(s)
their efficiency. Compared to an internal combustion As the PbSO4 precipitate forms, it coats both the electrodes,
engine (25% efficient) and a steam engine (35% efficient), which reduces the efficiency of the battery. The equation
the H2/O2 cell can operate at an efficiency of 45%. Owing for the overall reaction is:
to this high efficiency, coupled with the fact that they
are pollution-free, many possible developments and uses Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
for fuel cells have been proposed as alternative energy When recharging the battery: the reverse reaction occurs.
resources as well as solutions to current energy problems. Since a PbSO4 build-up is responsible for the reduction
Such propositions include their use in homes, industries in the cell’s efficiency, the reaction that produces this
and vehicles as a means of generating electricity and power. precipitate is reversed, thereby restoring the battery to
Apollo Moon vehicles and the American Gemini Space its original condition. This restoration process essentially
probes used fuel cells as their primary source of electrical involves converting the PbSO4 back into Pb on the anode
energy. They are also used in spacecraft to provide drinking
water, heat and electricity for astronauts. ITQ 10 In the operation of a lead–acid battery, lead exists in three
oxidation states. List these states.
Chapter 12 Redox equilibria 123

and back into PbO2 on the cathode. This is achieved with


the help of the alternator in the vehicle, which passes
an electric current through the battery in the opposite
direction of the cell reactions.
As the battery discharges for a long time, the concentration
of sulfuric acid decreases. Over a long period of time, the fine
PbSO4 precipitate forms a coarse, inert and non-reversible
layer. In this case, recharging the battery cannot restore it
to its original condition. A modern lead–acid battery lasts
for about four years or more.

Summary
✓ Oxidation is the removal of electrons from a ✓ A system with a more negative potential than
substance. another will act as a reducing agent towards it.
✓ Reduction is the addition of electrons to a ✓ A system with a more positive potential than
substance. another will act as an oxidizing agent towards it.
✓ Oxidation/reduction (‘redox’) reactions involve ✓ Electrode potential measurements give no
the transfer of electrons between substances. information about rates of reactions.
✓ The tendency of a substance to gain (or lose) ✓ The flow of electrons in a redox system is an
electrons in an aqueous system is measured by electric current and can do electrical work.
its standard electrode potential.
✓ A redox system in which electron flow is
✓ The more negative the standard electrode prevented can act as a storage cell.
potential, the better reducing agent the
substance is.
✓ Standard electrode potentials are measured
against that of the standard hydrogen electrode,
which is given the value 0.00 V.

Review questions
1 John tries to determine the electrode potential for The experiment fails to produce any results. However,
MnO4−(aq)/Mn2+(aq) using the set-up shown in if a few modifications are made, the experiment
Figure 12.12. would be successful.
(a) Define the term ‘standard electrode potential’.
Pt wire (b) What are THREE modifications that need to be
made to the apparatus in Figure 12.12 in order
to measure the standard cell potential of a cell
Fe
comprising an Fe2+(aq)/Fe(s) half-cell and an
MnO4−(aq)/Mn2+(aq) half-cell?
(c) Write equations for the reactions occurring in each
half-cell of the cell indicated in part (b) and hence
1.0 mol dm–3 FeSO4(aq) 1.0 mol dm–3 KMnO4(aq)
write an equation for the overall reaction that
Figure 12.12 Apparatus for determining standard electrode occurs.
potential.
124 Unit 1 Module 2 Kinetics and equilibria

(d) Calculate the standard cell potential, E cell , for the 4 (a) (i) Define the term ‘standard electrode potential’.
cell. (ii) State one use of standard electrode potentials.
(e) Determine one metal that produces an E cell (iii) Draw a labelled diagram to describe how the
greater than that produced by Fe. standard electrode potential of the Fe3+(aq)/
(f) Determine one metal that produces an E cell less Fe2+(aq) half-cell can be determined.
than that produced by Fe. (iv) Write the equation for the reaction occurring
(g) What effect (if any) would replacing the in each half-cell.
1.00 mol dm−3 FeSO4 with a 2.00 mol dm−3 FeSO4 (b) (i) Write a balanced equation for the reaction
solution have on the E cell value calculated in between aqueous Fe2+(aq) and acidified
part (d). Explain your answer. manganate(VII) ions.
(h) Draw a fully labelled diagram of the apparatus (ii) Calculate the e.m.f. of the cell represented by
needed to measure the standard electrode this reaction.
potential for MnO4−(aq)/Mn2+(aq) and indicate on (c) Consider the cell represented below:
your diagram the direction of electron flow in the Zn(s) | Zn2+(aq) || Ag+(aq) | Ag(s)
external circuit. (i) Write the equation for the reaction occurring
at the silver half-cell.
2 Which of the two cells described below produces the
(ii) Explain the effect of an increase in
larger potential difference? Show how you arrived at
concentration of Zn2+(aq) on the e.m.f. of the
your answer.
cell.
CELL I Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
(d) Discuss the feasibility of the reaction below:
CELL II Co(s) | Co2+(aq) || Ag+(aq) | Ag(s)
Ni2+(aq) + 2Cl−(aq) → Ni(s) + Cl2(g)
Predict which one of the metals above, if any, is
5 A Zn2+(aq)/Zn(s) half-cell is connected to a Ag+(aq)/
capable of reducing Sn4+ to Sn2+.
Ag(s) half-cell as shown below.
Sn4+ + 2e− ҡ Sn2+ E = +0.15 V
Zn(s) | Zn2+(aq) || Ag+(aq) | Ag(s)
3 (a) Use the following electrochemical data to (a) Write the equations for the reactions occurring at
construct the labelled cell diagram for the each half-cell.
combined half-cells. (b) Calculate the standard e.m.f. of the cell.
Cu2+/Cu E = +0.34 V (c) David sets up the Ag+(aq)/Ag(s) half-cell using
+
Ag /Ag E = +0.80 V a solution of 0.1 mol dm−3 Ag+ instead of
(b) Write the relevant half-equations for the changes 1.0 mol dm−3. Suggest how this would affect the
taking place at the anode and cathode. e.m.f. of the cell. Give a reason for your answer.
(c) Write the equation for the overall cell reaction. 6 The lead storage battery that is used in motor vehicles
(d) At which electrode in the electrochemical cell is one of the most common and useful batteries.
does reduction take place? Give a reason for your Anode – made of lead
answer. Cathode – made of lead(IV) oxide (PbO2)
(e) Calculate the cell potential. Electrolyte – sulfuric acid
(f) (i) Describe three changes you would observe (a) (i) Write the equations for the reactions occurring
if you replaced the Ag half-cell with a Zn at each electrode during discharge.
half-cell in the cell diagram in part (a). (ii) Calculate the standard cell potential.
(ii) Suggest one reason for the changes observed (b) A primary source of electrical supply on the
in (f)(i). Apollo moon flights was the fuel cell (H2/O2).
(iii) Identify an electrolyte that could be used in Such a cell uses porous electrodes into which
the zinc half-cell. streams of hydrogen (at the anode) and oxygen
(at the cathode) are introduced. Deduce the
useful by-product of the reaction. Include relevant
equations.
Chapter 12 Redox equilibria 125

Answers to ITQs Answers to Review questions


1 Zinc is the anode/negative electrode; placed on 1 (c) Anode reaction: Fe(s) − 2e− → Fe2+(aq)
the left of the cell. Copper is the cathode/positive Cathode reaction: MnO4−(aq) + 8H+(aq) + 5e− →
electrode; placed on the right. Electrons are negatively Mn2+(aq) + 4H2O(l)
charged and will tend to flow away from the negative Overall cell reaction:
electrode and towards the positive electrode in the 5Fe(s) + 2MnO4−(aq) + 16H+(aq) →
cell. Hence electrons flow from left to right. Fe2+(aq) + 2Mn2+(aq) + 8H2O(l)
2 (a) (d) E cell = +1.95 V
high-resistance voltmeter
3 (b) Anode reaction: Cu(s) − 2e− → Cu2+(aq)
V
Cathode reaction: 2Ag+(aq) + 2e− → 2Ag(s)
H2(g) at 298 K (c) Overall cell reaction: Cu(s) + 2Ag+(aq) →
and 1 atm
salt bridge zinc strip
Cu2+(aq) + 2Ag(s)
acid solution
(e) E cell = +0.46 V
containing
1.0 mol dm–3 4 (a) (iv) Anode reaction: H2(g) + 2e− → 2H+(aq)
H+(aq)
solution of Cathode reaction: Cu2+(aq) + 2e− → Cu(s)
Zn2+(aq)
(1.0 mol dm–3 )
(b) (i) 5Fe2+(aq) + MnO4−(aq) + 8H+(aq) →
platinum
electrode
5Fe3+(aq) + Mn2+(aq) + 4H2O(l)
(ii) E cell = +0.74 V
(b) The standard hydrogen electrode is the positive (c) (i) Ag+(aq) + e− → Ag(s)
electrode. 5 (a) Anode reaction: Zn(s) − 2e− → Zn2+(aq)
(c) Electrons flow from right to left. Cathode reaction: Ag+(aq) + e− → Ag(s)
3 YES because E for I−/I2 (+0.54 V) is less positive (b) E cell = +1.56 V
that that for Cl−/Cl2 (+1.36 V) so chlorine is a better 6 (a) (i) Anode reaction: Pb(s) → Pb2+(aq) + 2e−
oxidizing agent than iodine. Cathode reaction: PbO2(s) + 4H+(aq) + 2e− →
4 Zinc. Pb2+(aq) + 2H2O(l)
(ii) E cell = 1.82 V
5 (a) Electromotive force, e.m.f.
(b) Cu acts as the negative electrode.
(c) E = (−0.34) + (+0.80) = +0.46 V
6 E = (+1.66) + (−0.34) = +1.32 V. The positive e.m.f.
value of +1.32 V indicates that the reaction is feasible.
However, the rate of this reaction is very slow and
does not take place unless a small amount of NaCl is
added to the solution of Cu2+ ions.
7 Increase the concentration of the Cu2+(aq) ions, which
will shift the equilibrium to the right
Cu2+(aq) + 2e− ҡ Cu(s)
8 A dry cell does not contain any sloshing liquid that
might leak or drip when inverted or handled roughly.
9 Dry ammonium chloride will not conduct electricity.
The electrolyte is used as a paste so that enough
moisture is provided to allow the current to flow.
10 0 (in Pb), +2 (in PbSO4) and +4 (in PbO2).
126

Module 3
Chemistry of the elements

Chapter 13
Elements and periodicity: period 3
Learning objectives
■ Describe the variations in physical properties of the period 3 elements in terms of structure and
bonding.
■ Describe the reactions of the elements with oxygen, water and chlorine.
■ Predict the types of chemical bonding present in the oxides and chlorides.
■ Describe the reactions of the oxides and chlorides with water.
■ Explain the trend in acid/base behaviour of the oxides and chlorides.

Introduction
The arrangement of elements in the periodic table reveals The physical properties of the elements vary throughout
that a considerable number of physical and chemical the periodic table and these properties may be divided into
properties of these elements vary periodically with atomic two categories: atomic properties and bulk properties.
number. This concept of ‘periodicity’ embodied in the Atomic properties depend only upon the structure of the
periodic table has facilitated rapid progress in understanding atoms, and any variation in the properties may be explained
the properties of all the elements. On account of this, purely in terms of single isolated atoms. Bulk properties,
the periodic table has been extremely instrumental in however, not only depend on the characteristics of the
the classification and arrangement of our accumulated separate atoms, but also on how they are linked or packed
chemical knowledge. together into the structure of the element.
This chapter serves to highlight some of the properties of
the period 3 elements, as shown in Figure 13.1.
elemental properties

Atomic properties
atomic bulk
Electronic configuration
depend on depend on structure The atomic number gives the number of electrons in an
structure only and bonding atom. From this we can work out the arrangement of
the electrons in an atom, which is called the electronic
electronic configuration melting point
configuration. Table 13.1 shows the shortened version
atomic radii electrical conductivity of the electronic configurations of the eight elements in
ionic radii density period 3 of the periodic table. We can see that:

ionization energy ■ the 3s and 3p sub-levels are being filled with electrons;
■ the elements have the same number of electrons in
electronegativity
their inner shells – they all have the [Ne] structure;
Figure 13.1 Atomic and bulk properties of the elements. ■ the number of valence electrons increases.
Chapter 13 Elements and periodicity: period 3 127

Table 13.1 Electronic configurations of the period 3 elements ■ Covalent or metallic radius – half the shortest
Element Electronic configuration internuclear distance between similar atoms either
Na [Ne] 3s1 joined by a covalent bond or in a metallic crystal lattice
Mg [Ne] 3s2 (Figure 13.2b). Covalent radius may be measured for
Al [Ne] 3s2 3px1 most elements, since even metals in the vapour phase
Si [Ne] 3s2 3px1 3py1 often exist as diatomic molecules. Metallic radius is
P [Ne] 3s2 3px1 3py1 3pz1 restricted to those elements which form metallic lattices.
S [Ne] 3s2 3px2 3py1 3pz1 Clearly, the type of bonding will influence the size of the
Cl [Ne] 3s2 3px2 3py2 3pz1 atom. Hence, the various atomic radii will have different
Ar [Ne] 3s2 3px2 3py2 3pz2 values for the same element. Generally, the covalent radius
It is these valence electrons that determine the structure, is the smallest and the van der Waals radius is the largest.
bonding and properties of the elements. For instance, the covalent radius for Na is 0.157 nm and
the metallic radius is 0.186 nm. When chemists speak of
Atomic radii atomic radii, they usually refer to covalent radii.

You will remember from your basic geometry that the radius Regardless of the measure of atomic radius that is chosen,
of a circle is defined as the distance between the centre of the general trend across period 3 remains the same. The
the circle and its circumference. Assuming that an atom is two primary factors that affect the atomic radius are:
circular in shape, the atomic radius may be defined as the ■ the size of the charge on the nucleus; and
distance between the centre of the nucleus and the outermost ■ the number of shells between the nucleus and the
electron (valence) shell. However, according to quantum outermost electrons (inner shells).
theory (see Chapter 2), there is no well-defined ‘outer- As you go along period 3 from left to right, electrons are
edge’ valence shell since valence electrons do not reside in going into the same main outer shell and therefore the
a specific orbit. Rather, an atom’s electrons are described as number of inner shells remains the same. However, due to
occupying regions of space (i.e. atomic orbitals), which are the increase in the number of protons in the nucleus, the
given by a probability distribution. As a consequence, the nuclear charge increases. The resultant effect can be seen
size of an atom is difficult to define and measure accurately. in Figure 13.3.
There are different ways to define the size of an atom; 0.20
the definition depends on both the method used and the
conditions under which they are measured. Consider an 0.18
Atomic radius / nm

automobile tyre: the radius of the tyre is different when 0.16


measured to the top of the tyre than when measured to the
bottom of the tyre resting on the ground. The former value 0.14

will be greater than the latter. In much the same way, the 0.12
radius of an atom will vary depending on whether it is free,
or bonded to other atoms – different values for the sizes of 0.10

atoms are obtained. 0.08


Na Mg Al Si P S Cl
■ van der Waals radius – half the internuclear distance Element
between non-bonded similar atoms at their closest
Figure 13.3 Atomic radii of the elements from period 3. The pull
approach (Figure 13.2a). This is most easily determined of the nucleus on the outermost electrons increases, resulting in
for non-metals, and is particularly useful for the noble a decrease in atomic radius.
gases as they do not form chemical bonds.
a b
Ionic radii
Like the atomic radius, the ionic radius is determined
by measuring the internuclear distance between adjacent
nuclei. This distance gives the sum of the radii of the cation
and anion. By comparing the internuclear distances for
2r 2r
a range of compounds, the radii of individual ions are
Figure 13.2 (a) van der Waals radius; (b) covalent or metallic established.
radius.
128 Unit 1 Module 3 Chemistry of the elements

Before we describe the trend in ionic radius across period 3, Figure 13.4 summarizes this data.
we must first appreciate a couple of points. 0.25

Elements to the left of period 3 (Na, Mg, Al) are metals


0.20

Ionic radius / nm
and hence lose electrons to form cations. Cations are
always smaller than their parent atoms. A cation has fewer 0.15
electrons than the atom and so the nucleus attracts the
remaining electrons more strongly, causing a reduction in 0.10

size.
0.05
Elements to the right of period 3 (P, S, Cl) are non-metals
0
and tend to gain electrons to form anions. Anions are Na+ Mg 2+ Al 3+ P3– S 2– Cl –
always larger than their parent atoms. An anion has more Period 3 ions

electrons than the atom and so the attraction of the nucleus Figure 13.4 Ionic radii for period 3. Note the decreases at the left
for each electron is reduced, resulting in expansion. and the right of the period and the large jump in the centre.

The trend in ionic radii across period 3 shows:


First ionization energy
■ a decrease in ionic radii for the cations of Na, Mg and Al;
In general, the ease with which an atom loses electrons
■ a decrease in ionic radii for the anions of P, S and Cl; to form a cation describes the ionization energy of the
■ a large jump in ionic radii between Al3+ and P3−. atom. First ionization energy is defined as the energy
When thinking about Na+, Mg2+ and Al3+, each resulting required to remove the most loosely held electron from a
cation has the same electronic configuration as neon; neutral atom in the gaseous state to form a cation.
they are isoelectronic. However, the number of protons Na(g) − e− → Na+(g)
is increasing. This increases the nuclear attraction on the
This equation is more commonly written as
remaining electrons. Therefore, the size of the metallic ion
decreases across the period (Table 13.2). Na(g) → Na+(g) + e−
Table 13.2 Cationic radii for period 3 1600
First ionization energy / kJ mol –1

Cation Na+ Mg2+ Al3+ 1400


Number of protons 11 12 13 1200
Electronic configuration of ion 2,8 2,8 2,8
1000
Ionic radius / nm 0.102 0.072 0.054
800

When thinking about P3−, S2− and Cl−, the anions are 600

isoelectronic with argon. There is now an extra inner shell 400

of electrons. However, the progressively larger nuclear 200


charge exerts a greater force of attraction on the valence 0
Na Mg Al Si P S Cl Ar
shell electrons. As a result, the size of the anion decreases
Element
(Table 13.3).
Figure 13.5 The change in first ionization energy across period 3.
Table 13.3 Anionic radii
There is a general increase in the first ionization energy
Anion P3− S2− Cl−
across a period, as can be seen from Figure 13.5. On passing
Number of protons 15 16 17
across a period, the nuclear charge steadily increases and the
Electronic configuration of ion 2,8,8 2,8,8 2,8,8
atomic radius falls. Both of these factors result in an increase
Ionic radius / nm 0.212 0.184 0.181
in nuclear attraction, which means that the electrons are
You should also notice the big jump in ionic radius between held more tightly. This results in an increase in ionization
Al3+ (0.054 nm) and P3− (0.212 nm). This huge disparity is energy across a period. If the electron is held more tightly,
attributed to the addition of an inner shell of electrons. it is harder to pull away and thus more energy is required.

ITQ 1 Suggest a second reason for the ITQ 2 Describe the relationship between ITQ 3 Suggest two other pairs of elements
reduction in radius going from Na to Na+ atomic radius and first ionization energy. which should exhibit differences in their first
other than Na+ having fewer electrons. ionization energies as Mg/Al and P/S.
Chapter 13 Elements and periodicity: period 3 129

The ionization energy does not increase smoothly on passing of an atom is expressed relative to a standard. The standard
across period 3. There are two irregularities, which occur at used is fluorine – the most electronegative element – which
aluminium and sulfur, and these can be explained on the is assigned an electronegativity of 4.0.
basis of sub-levels. Let us look at each irregularity in turn. Figure 13.6 shows a graph of electronegativity values
The first ionization energy of aluminium is smaller than plotted against atomic number for the elements Na to Cl.
magnesium (Table 13.4). The outermost electron of As the atomic radius decreases across the period (see Figure
magnesium is located in a filled 3s orbital, which is relatively 13.3), the attractive force of the nucleus is felt more strongly
close to the nucleus. However, aluminium’s outermost by the electrons in the bond. As a result, electronegativity
electron is unpaired, resides further away from the nucleus increases across a period.
in a 3p orbital and is partially screened by the 3s electrons.
Therefore, it requires less energy to remove the less tightly Bulk properties
held, unpaired 3px1 electron in aluminium than it is to
remove an electron from the filled 3s orbital in magnesium. Melting point
Table 13.4 Comparing the first ionization energies for Mg and Al The melting point of a substance may be defined as the
Electronic configuration ΔHi1 / kJ mol−1 temperature at which the pure solid breaks down and is
magnesium [Ne] 3s2 738 in equilibrium with pure liquid at standard atmospheric
aluminium [Ne] 3s2 3px1 578 pressure. Melting points depend on both the structure and
bonding in a substance. More specifically, there are four
The first ionization energy of sulfur is smaller than factors which influence the melting point:
phosphorus (Table 13.5). For both sulfur and phosphorus,
■ the type of forces holding the solid state together,
the electron is being removed from the same orbital and
whether they are ionic, covalent, metallic or van der
the screening is identical. In the case of phosphorus, the
Waals;
three electrons in the 3p orbitals all have parallel spins.
However, in sulfur, the electron being removed is one of ■ the strength of attraction between the particles in the

the 3px2 pair. The repulsion between the two electrons in structure;
the same orbital makes this electron easier to remove. ■ the stability of the lattice;

Table 13.5 Comparing the first ionization energies for P and S ■ the size of the molecule.

Electronic configuration ΔHi1 / kJ mol−1 2000

phosphorus [Ne] 3s2 3px1 3py1 3pz1 1012


sulfur [Ne] 3s2 3px2 3py1 3pz1 1000 1500
Melting point / K

Electronegativity 1000
3.5
Pauling electronegativity value

3.0 500

2.5

2.0 0
Na Mg Al Si P S Cl Ar
Element
1.5
Figure 13.7 A graph of melting point for period 3.
1.0
As period 3 is traversed from sodium to argon, the melting
0.5
point generally rises sharply from sodium through to silicon
0
Na Mg Al Si P S Cl
(Figure 13.7). It then undergoes a rapid fall between silicon
Element and phosphorus. Between phosphorus and argon there is a
Figure 13.6 Change in electronegativity across period 3. general decrease in the melting point. These trends may be
explained in more detail.
The electronegativity of an atom provides a numerical
measure of the power of an atom to attract electron pairs ■ Sodium, magnesium and aluminium are metals and
to itself in a covalent bond. Electronegativity cannot be hence exhibit metallic bonding in which electrostatic
measured directly. As a result, Pauling devised a system called attractive forces exist between the positively charged
the electronegativity scale, in which the electronegativity metals ions and a ‘sea’ of delocalized electrons. On
130 Unit 1 Module 3 Chemistry of the elements

moving from sodium to aluminium, the charge on the The trend in electrical conductivity across period 3 elements
metal ion increases from +1 to +3 and therefore the shows a dramatic increase between sodium and aluminium,
number of delocalized electrons increases. With the followed by a drastic fall at silicon; the remaining elements
nuclei getting more positively charged and the ‘sea’ do not conduct electricity (Figure 13.9). These trends can
getting more negatively charged, the strength of the be explained on the same basis that was used to explain
attraction increases which causes an increase in the melting point.
strength of the metallic bond and hence the melting 1.0
point increases.

Relative electrical conductivity


0.9
■ Silicon is a metalloid, showing both metallic and 0.8
non-metallic properties. Silicon forms a giant three- 0.7

dimensional lattice structure similar to that of 0.6


0.5
diamond. Each silicon atom is covalently bonded to
0.4
four other silicon atoms in a tetrahedral arrangement.
0.3
Considerable energy is required to break these bonds,
0.2
so the melting point of silicon is very high. 0.1
■ Phosphorus, sulfur and chlorine are non-metals 0
Na Mg Al Si P S Cl Ar
and their structures contain simple, small covalent Element
molecules held together only by weak van der Waals
Figure 13.9 Relative electrical conductivity of the period 3
forces of attraction. As a result of such weak forces, the elements (Al = 1.00).
melting points of these elements are low since little
■ Sodium, magnesium and aluminium are metals and
energy is required to overcome them.
hence exhibit metallic bonding in which positive
■ Argon is a noble gas and therefore exists as individual
metal ions are attracted to delocalized electrons. These
argon atoms. The extent of van der Waals attractions is
delocalized electrons serve as mobile charge carriers.
very limited and so the melting point is extremely low.
In going from sodium to aluminium, the number
When thinking about phosphorus, sulfur and chlorine, the of mobile delocalized electrons increases. Therefore
magnitude of their melting points are governed entirely there are more charge carriers and so the electrical
by the size of the molecules (Figure 13.8). The larger the conductivity increases.
molecule, the more van der Waals forces present and hence ■ Silicon is a metalloid and is a semiconductor; the full
the greater the melting point. explanation for this semiconductivity is beyond the
■ Sulfur has the highest melting point; it exists as S8 scope of the CAPE syllabus. We should know that
molecules. within the tetrahedral structure, the four electrons in
■ Phosphorus has the next highest; it exists as P4 each silicon atom are held strongly in covalent bonds.
molecules. However, there are a few delocalized electrons which
■ Chlorine has the lowest melting point; it exists as Cl2 accounts for the poor conductivity of silicon. Unlike a
molecules. true metal, the conductivity increases with an increase
in temperature.
■ Phosphorus, sulfur, chlorine and argon are non-metals
and do not conduct electricity because there are no
S8 P4 Cl2 free delocalized electrons within their structures to
Figure 13.8 S8, P4 and Cl2 molecules. convey an electric current. In phosphorus, sulfur and
chlorine the outer electrons are not free to move and
Electrical conductivity carry charge because they are held strongly in covalent
bonds. In argon, the outer electrons are not free to
Electrical conductivity is a measure of a material’s
move and carry charge because they are held strongly
ability to conduct an electric current. An electric current
in a stable third energy level.
may be described as a flow of electric charge and, as such,
an element can conduct electricity provided that it contains
ITQ 4 Carbon exists as graphite and as diamond (allotropes).
electrons (charge carriers) that are free to move. Generally,
Graphite is an excellent conductor of heat and electricity whereas
metals are good conductors of electricity whilst non-metals diamond is an insulator. What does this suggest about the
are poor conductors. electron arrangement in the two allotropes?
Chapter 13 Elements and periodicity: period 3 131

Table 13.6 Period 3 elements and their reactions with oxygen, water and chlorine
Element Reaction with oxygen Reaction with water Reaction with chlorine
Na burns with an orange flame, producing a mixture of an exothermic reaction with cold water, producing burns with a bright orange flame, producing NaCl
Na2O and Na2O2 NaOH and H2
Mg burns with a brilliant white flame, producing MgO reacts slowly with cold water, giving Mg(OH)2 and H2, burns with an intense white flame, giving MgCl2
but exothermically with steam, giving MgO and