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Physical
CHEMISTRY
Physical chemistry seeks to uncover the underlying principles
of chemistry. Our ideas were transformed by the discovery just
over a hundred years ago of the electron (see chapter 2).
Recently, such spectacular images as those on the right have
provided experimental confirmation of the wave nature of
electrons when they are within atoms. This idea led to a
thorough understanding of the structure of atoms and of the
bonding between atoms (see chapters 3–5).
Bonding theory explains the structure of elements and
compounds; structure and bonding together can explain the
physical properties of substances, such as their melting and
boiling points and their conductivities (see chapters 6 and 7).
Gases (chapter 8) complete our survey of the behaviour of
individual chemicals on their own.
We begin our study of chemical reactions in chapter 9 with
an account of the masses and volumes of chemicals that react.
This is followed by a discussion of the energy changes that
accompany chemical reactions (chapter 10). The focus then
shifts in a set of four chapters (11–14) to an investigation of
competition between substances. This involves the general
study of equilibrium followed by an examination of the two
This image shows a ring of 48 iron
major classes of chemical reaction: acid–base and redox atoms on a copper surface. The
reactions. These four chapters conclude with an overview of electrons in the surface scatter
the nature of spontaneous change towards equilibrium. from the iron atoms. The ring of
iron atoms forms a boundary, or
The final chapter in the physical chemistry section of the ‘corral’, which traps electrons in its
book (chapter 15) considers chemical kinetics. A reaction that interior. The trapped electrons
is predicted by thermodynamics to be spontaneous may be too occupy the quantum states of the
corral. Quantum corrals provide us
slow to be of any economic value. To investigate whether any with an opportunity to visualize the
particular substance is stable or not, we need to consider both quantum behaviour of electrons in
thermodynamic stability and kinetic stability. small confining structures.
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P H YS I C A L C H E M I S T RY
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1
1.1
O B J E C T I V E S
• The origins and scope of chemistry
Iron extraction uses chemical
techniques discovered more than 3000
years ago. Converting iron into steel
became much cheaper in the
nineteenth century.
12
Page 12
Patterns in chemistry
Human beings are naturally inquisitive. We have progressed from the
Bronze Age to our current state of technological ability in just 5000 years.
Throughout that time we have constantly observed the world around us and
asked the questions: ‘Why does that happen?’ and ‘How can I control what
happens?’ We try to answer these questions by carrying out experiments
and searching for patterns in what we see and measure. Chemists are
concerned with the study of matter – the structure of materials and how
they interact. Chemistry aims to explain patterns in the behaviour of
materials by formulating rules, theories, and laws to reveal the underlying
nature of matter.
AN INTRODUCTION TO CHEMISTRY
Chemistry is the study of the elements and the compounds formed when
they bond with each other. The subject is subdivided into three main
branches: physical chemistry, inorganic chemistry, and organic
chemistry. Physical chemistry is concerned with how the chemical
structure of a substance affects its properties. It includes the study of
chemical bonding and the structures of solids, liquids, and gases.
Physical chemistry also investigates energy changes that accompany
chemical reactions and how fast reactions happen. Inorganic chemistry
is concerned with describing the properties and reactions of all elements
and compounds other than those of carbon. Organic chemistry is
concerned with the chemistry of carbon compounds. Its study centres
particularly on the ability of carbon atoms to join with each other to
form rings and long chains. There are also related branches of chemistry
such as biochemistry, chemical engineering, and geochemistry.
The origins of chemistry
The earliest uses of chemical processes were in the extraction of metals
such as copper and iron, the firing of clays and sands to make ceramics
and glasses, and the extraction and use of dyes. People were able to do
all these things, but how could they explain what they saw happening?
When thinking about the material world, people have always tried to find
patterns and describe rules of behaviour. For example, when faced with
sorting out a box of jumbled objects, the first thing anyone might try to
do is sort them into groups of similar things. In the case of a collection
of coloured marbles, a suitable procedure would be to sort them into
different colours or sizes. The same was true of people at the dawn of
civilization as they searched for a way of sorting out and explaining the
non-living world around them.
At first, in the fifth century BC, their sorting was very broad. They
concluded that there were four main categories of substance: fire, air,
water, and earth. Each of these four categories was composed of pairs of
the four fundamental qualities: hot, cold, wet, and dry. Everything in the
whole of the non-living world had to fit one of these categories or a
combination of them. At a simple level this classification works:
mountains, deserts, rocks, and houses are all ‘earthy’; all liquids are
‘watery’; all gases are ‘airy’; and all flames are ‘fiery’. This scheme can also
explain changes in materials. For example, when (cold–wet) water is
boiled, the result is a form of (hot–wet) air, i.e. steam.
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PAT T E R N S I N C H E M I S T RY

The early alchemists Paracelsus

The systematic study of chemistry as a subject started in Egypt about
Theophrastus Bombast von
1700 years ago. Writings by Zosimos (c. AD 300) describe chemical
Hohenheim (c. 1493–1541), a Swiss
experiments and chemical apparatus. For the next thousand years, most physician who called himself
chemical exploration sought ways of changing (or transmuting) cheap Paracelsus, attempted to move
base metals such as lead into the precious metals, gold or silver. This alchemy beyond simply striving to
work on transmutation was called alchemy (from the Arabic al-kimia: transmute metals. He declared that an
equally valid aim for alchemists was
al = the, kimia = art of transmuting metals).
to try to cure illness using chemicals
They did not succeed in their search but, almost accidentally, they as remedies. At that time four fluids
developed many sound techniques of chemical manipulation. Modern of the human body called humours
chemistry was born during the seventeenth century when some of these were thought to determine a person’s
physical and mental state. However,
early scientists started to investigate the mechanisms by which
Paracelsus believed illness arose from
substances were changed. Alchemists continued their work during this specific external causes rather than
period of transition, but their use of ghostly spirits and ‘uncorporeal from an imbalance of the humours.
bodies’ to explain their findings was gradually seen to make no sense.

The discovery of phosphorus in 1669 resulted from the alchemical investigations of

Hennig Brandt of Hamburg. Brandt’s starting material was urine. Phosphorus emits
light (it is luminescent) by reaction with air; its name comes from the Greek for
‘bringer of light’.

The foundation of modern chemistry

During the seventeenth century, the study of chemistry began to
concentrate on the preparation, isolation, and use of new substances. In
1661, Robert Boyle wrote a landmark book called The Sceptical Chymist,
in which he attacked the idea of the four categories (fire, air, water, and
earth) and introduced the modern concept of chemical elements. During
the following two centuries, Boyle’s ideas took root and slowly developed.
In 1789, in his Elementary Treatise on Chemistry, Antoine Lavoisier
published a list of 33 chemical elements, many of which we recognize
today. At that time, an element was thought of as a substance that cannot
Antoine Lavoisier was the founder of
be broken down into two or more simpler substances. We know now that modern chemistry. He showed that air
an element is a substance that contains only one sort of atom, and that contains oxygen and that water is a
compound of oxygen and hydrogen. In
an atom is the smallest particle of an element that can exist 1789, using Boyle’s definition of an
independently. Most of our modern chemical understanding rests on element, he drew up the first table of
these two simple and fundamental points. chemical elements. This portrait is by
Jacques-Louis David.
SUMMARY
• An element is a substance that cannot be broken down into two or
more simpler substances.
• An element is a substance that contains only one sort of atom.
• An atom is the smallest particle of an element that can exist
independently.

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1.2 E LEMENTS : THE SEARCH FOR PATTERNS

O B J E C T I V E S

• Nineteenth-century attempts at
classification
Atomic mass
During the nineteenth century, the
atomic masses of elements were
calculated relative to hydrogen. One
atom of this element was used as the
arbitrary unit of mass. On this scale,
oxygen had an atomic mass of 16,
indicating that one atom of oxygen
had a mass equal to the total mass of
16 atoms of hydrogen. The atomic
mass for each element was calculated
from carefully measuring the
quantities of reactants and products
involved in chemical reactions.
Atomic masses are now measured
relative to one-twelfth of the mass of
one atom of carbon-12, as we shall
see later.
If you were a chemist working during the 1800s, you would have been
living in exciting times. New elements were being discovered at an
amazing rate. In 1807 Humphry Davy used electrolysis to isolate the new
metals sodium and potassium. In 1808 he isolated the metals calcium,
strontium, and barium. In 1810, Davy went on to show that chlorine is
an element similar to iodine. During this period, chemists also began to
investigate the quantities in which elements reacted with each other.
From these investigations, each element was assigned an atomic mass.
Döbereiner’s triads
With about fifty elements clearly identified, chemists tried to group
together elements that resembled each other. Following the process of
classification started by the Ancient Greeks, they were looking for an
underlying theory that would arrange elements into groups and explain
their properties. The first real success came in 1817 when Johann
Döbereiner noted that the metals calcium, strontium, and barium were
very alike.
A decade later, once bromine had been discovered, he saw that the
non-metals chlorine, bromine, and iodine were also very similar.
Döbereiner also noted that the atomic mass of the middle element of
each three was approximately the average of the atomic masses of the
outer two elements. However, he was not able to suggest why this was so.
Döbereiner believed that elements could be arranged in threes, or triads
as he called them; but he could not find enough triads to construct a
convincing theory to explain his classification.

Element Atomic mass

Calcium 40.1
Strontium 87.6
Barium 137.3

Sulphur 32.1
Selenium 79.0
Tellurium 127.6

Chlorine 35.5
Bromine 79.9
Iodine 126.9

Three of Döbereiner’s triads. In each

triad, the atomic mass of the middle
element falls approximately mid-way
between the atomic masses of the outer
two elements.

A Döbereiner triad. Chlorine, bromine, and iodine are all non–metals. Bromine (left)
is a liquid with a brown vapour; chlorine (centre) is a gas; iodine (right) is a solid with
a purple vapour. The atomic mass of bromine (79.9) is approximately equal to the
average of the atomic masses of chlorine (35.5) and iodine (126.9) (the calculated
average is 81.2).

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PAT T E R N S I N C H E M I S T RY

Alexandre Béguyer de Chancourtois

In 1862, the French geologist Alexandre Béguyer de Chancourtois
arranged the names of the elements in order of increasing atomic mass
in a helical pattern around a cylinder. This procedure divided the
elements into vertical columns. Each column contained some elements
with similar properties. For example, lithium, sodium, and potassium
appeared in one column; and oxygen, sulphur, selenium, and tellurium in
another. (One problem was that he included some compounds and alloys
thought to be elements at the time.) Béguyer de Chancourtois concluded
that: ‘The properties of substances are the properties of numbers.’ His
work was ignored by the majority of chemists, mainly because the
diagram explaining his idea was omitted from the published paper.

William Odling
In 1864, William Odling published an article entitled ‘On the
Proportional Numbers of the Elements’. He grouped certain elements
together and noticed that, for ‘well-defined groups’, their sequences of
chemical properties and their sequences of atomic masses went in
parallel with each other. Odling constructed a table of the elements to John Newlands
illustrate these relationships.
Like Odling, he was born in a district
Newlands’ octaves of London called Southwark.
Newlands’ law of octaves represented
John Newlands was the chief chemist in a London sugar refinery. In
an important step on the path to a
1865 he noticed that, if the elements were written in order of their systematic classification of the
atomic masses, similar chemical properties appeared at every eighth elements. However, his work was
element. Newlands likened this behaviour to a musical scale and ridiculed.
suggested that the elements obeyed a law of octaves. Newlands had When he presented his ideas to the
glimpsed the correct underlying pattern to the recurring properties of the Chemical Society in London, he was
asked ‘whether he had ever examined
elements, but he did not take the idea far enough. The real father of the
the elements according to the order of
modern periodic table was a Russian, Dmitri Mendeleyev. their initial letters?’, and he was told
that his work was ‘not adapted for
publication’. He did not receive the
SUMMARY credit he deserved.
• Döbereiner identified groups containing three elements with similar In later years it became clear that
properties. He called these groups triads. Newlands had anticipated
• The triads included calcium–strontium–barium and Mendeleyev’s 1869 periodic law.
Belatedly, Newlands was awarded the
chlorine–bromine–iodine. Davy Medal of the Royal Society in
• Newlands drew up a list of elements in order of increasing atomic 1887. A plaque was unveiled in 1998
mass and noted that every eighth element fell into a group with at Elephant and Castle, London, to
commemorate the centenary of his
similar chemical properties.
death.

PRACTICE
1 Look through this spread and list:
a the metals mentioned, and
b the non-metals mentioned.
2 Look up the following names and words in a
large encyclopedia or on a computer. Arrange
them into a sequence that shows the
development of chemistry.
a Bronze Age b Iron Age
c Alchemy d Elements
e Robert Boyle f Antoine Lavoisier
g Joseph Priestley h Paracelsus
i John Dalton.

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1.3 M ENDELEYEV ’ S PERIODIC TABLE

O B J E C T I V E S

• How Mendeleyev constructed the
first periodic table
Towards the end of the 1860s, chemists were on the verge of proposing a
grand unifying model that would account for the properties of the
elements. The 62 separate elements known in 1869 would soon be
grouped and classified according to a set of clear rules. Newlands and
others had glimpsed the underlying pattern in the properties of the
elements. However, their understanding was incomplete and fragmented.
It was the Russian Dmitri Mendeleyev who collected the elements
together in a table that revealed the periodic (repeating) pattern in their
properties.

The periodic law

We can arrange glass marbles systematically by referring to their colour
or size. Mendeleyev arranged the 62 elements then known by referring to
their atomic masses. Starting with hydrogen, he wrote out the elements
in horizontal rows, in order of increasing atomic mass. This gathered
elements with similar properties below one another in vertical groups.
Mendeleyev’s stroke of genius was to group elements according to their
properties, even if he had to move some elements out of the strict
sequence of increasing atomic mass. He looked at the arrangement of the
elements in his table and was then able to state his periodic law, as
follows:
• ‘The elements, if arranged according to their atomic masses, show an
evident periodicity of properties.’
A biographical note H

Dmitri Ivanovich Mendeleyev was Li Be B C N O

born in Tobolsk, Siberia, in 1834, the
youngest of fourteen children. Na Mg Al Si P S Cl
Mendeleyev became the most
K Ca Ti V Cr Mn Fe Co Ni Cu Zn As Se Br
celebrated chemist of his generation,
once the predictions he had made Rb Sr Y Zr Nb Mo Ru Rh Pd Ag Cd In Sn Sb Te I
were verified.
Cs Ba La Ta W Os Ir Pt Au Hg Tl Pb Bi
Mendeleyev had divorced his first
wife and then married a young art
student. According to Russian
Orthodox Law, he was a bigamist. No
action was taken as Tsar Alexander II
Ce Tb Er
rejected criticism of his behaviour by
saying: ‘Yes, Mendeleyev has two Th U
wives, but I have only one
Mendeleyev.’ A modern outline of the periodic table incorporating the 62 elements known to
Mendeleyev in 1869.

The shape of the periodic table

The illustration above shows the 62 elements known to Mendeleyev,
positioned on an outline of a modern form of the periodic table. His
original table successfully classified all the elements in Groups I to VII.
The elements now referred to as ‘transition metals’ were scattered
throughout the table in regions called ‘subgroups’. These elements were
later assigned to their own specific area created at the centre of the table.

Changing the order to fit the properties

The problem with arranging the elements in strict order of atomic mass
is that the pattern does not match the properties of all the elements. For
example, iodine ends up in the wrong place, away from bromine and
chlorine. Mendeleyev had the courage to use his knowledge of the
properties of the elements to bend his own rule; he simply exchanged
some positions on the basis that the atomic masses known at the time
might be inaccurate. Mendeleyev also had the foresight to realize that
some elements had yet to be discovered.

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PAT T E R N S I N C H E M I S T RY

The undiscovered elements

Having suggested that there must be undiscovered elements, Mendeleyev Property Eka–silicon, Germanium,
E Ge
left gaps for them in his table in order to preserve the principle of
(predicted) (observed)
periodicity. Most significantly, he went on to predict in detail the
chemical properties that these unknown elements would have. There was Atomic 72 72.6
a gap in his original table between silicon and tin, now occupied by mass

germanium. Mendeleyev inserted an element he called ‘eka-silicon’ into Density 5.5 g cm–3 5.35 g cm–3
this gap and he predicted its properties by inspection of the properties of
Oxide
the other elements in the group. The properties of germanium, isolated
nature white solid white solid
by Clemens Winkler in 1886, were in close agreement with Mendeleyev’s formula EO2 GeO2
predictions for eka-silicon. It is a further testimony to the brilliance of density 4.7 g cm–3 4.23 g cm–3
Mendeleyev’s ideas that the later discovery of a completely new group of
Chloride
elements, the noble gases, did not disrupt his overall scheme. boiling below 100 °C 84 °C
point
formula ECl4 GeCl4
density 1.9 g cm–3 1.84 g cm–3

The properties of eka-silicon suggested

by Mendeleyev compared with the
actual properties of germanium.

Rb

50

Atomic volume / cm3 mol–1

40
This stamp commemorates the centenary of the introduction of the periodic table by
Dmitri Mendeleyev. Gallium (Ga), unknown in 1869, is identified.
Sr
30
Lothar Meyer
Ca
As Mendeleyev was completing his periodic table, Lothar Meyer in Na
Germany was also working with the concept of periodicity. He 20
constructed a plot of the atomic volumes of the elements against their Mg
atomic masses. He calculated the atomic volume of each element by Li
10
dividing its atomic mass by its density. The overall shape of the plot
consisted of a series of periodically repeating peaks and troughs, Be

illustrating the periodic nature of the atomic volumes of the elements. 0

0 10 20 30 40 50 60 70 80 90
Relative atomic mass

SUMMARY Lothar Meyer’s curve of atomic volume

• Mendeleyev was able to obtain groups containing similar elements by against atomic mass would have looked
similar to this one. Notice the elements
arranging the elements in order of increasing atomic mass. at the peaks of the curve – lithium,
sodium, potassium, and rubidium.
• He left gaps or altered the order of the elements, to make better sense
of their properties.
• Elements discovered later fitted in to the gaps in the table; their
properties matched those predicted by Mendeleyev.

PRACTICE
1 Chemists greeted Mendeleyev’s periodic law,
which is only one sentence long, with a great
deal of enthusiasm and approval. Why did it
create so much excitement?
2 Why did the later discovery of the noble gases
(helium, neon, argon, krypton, xenon, and
radon) not affect the overall arrangement of
Mendeleyev’s periodic table?
3 Copy the outline of the periodic table given
opposite. Add to it the symbols of the elements
about whose chemistry you already know
something. Is your chemical knowledge scattered
randomly across the table or is there an
underlying pattern?
4 You may have completed most of a whole period
in question 3. Run your eye across it from left to
right. Do you notice any trend in a property of
the elements? Describe any trend that you see.

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