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Edexcel
Chemistry
Graham Hill
Andrew Hunt
for AS
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Artwork credits: Philip Allan Updates: Dr Eric Wolff, graph of estimated temperature difference from today and carbon dioxide and methane in ppmv
against year before, from Chemistry Review, volume 15, number 1 (September, 2005); Carbon Footprint Ltd: Redrawn pie chart showing components of a
typical footprint from (www.carbonfootprint.com/carbon_footprint.html); Chemicals Industries Association: Pie chart of products produced by the
chemical industry in the UK from www.cia.org.uk (Chemicals Industries Association, 2006); www.greener.industry.org: Diagram of manufacture of
ethanoic acid from carbon monoxide and ethanol from diagram of Reaction mechanism on screen 6 of the series of web pages on ethanoic acid; IPCC :
Graph of temperature differences from 1961-1990 average against year (redrawn) from Presentation of the Working Group 1 report
(www.ipcc.ch/present/presentations.htm); LGC: Vicki Barwick and Elizabeth Pritchard, extracts from Introducing Measurement Uncertainty (LCG, 2003), ©
LGC; Royal Society of Chemistry: Graph of carbon dioxide in ppmv against year AD from Education in Chemistry, volume 41, number 5 (September,
2004);Transport for London: Flow diagram of hydrogen-fuelled London bus and supply of hydrogen (slightly modified) from www.tfl.gov.uk.

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Contents

Unit 1 The Core Principles of Chemistry 1

1 Chemical quantities 2
2 Energetics 29
3 Atomic and electronic structure 45
4 Bonding and structure 63
5 Introduction to organic chemistry 83
6 Hydrocarbons: alkanes and alkenes 96

Unit 2 Application of Core Principles

of Chemistry 117
7 The shapes of molecules and ions 118
8 Polar bonds and polar molecules 127
9 Intermolecular forces 131
10 Redox 138
11 Groups in the periodic table 147
12 Chemical analysis 164
13 Kinetics 178
14 Chemical equilibrium 190
15 Alcohols and halogenoalkanes 199
16 Organic reaction mechanisms 211
17 Instrumental analysis 220
18 Green chemistry 225
19 Chemistry in the atmosphere 234
The periodic table of elements 244
Index 245
iii
 Introduction
Welcome to Edexcel Chemistry for AS. This book covers everything in the
Edexcel specification with 6 topics for Unit 1 and 13 topics for Unit 2. Test
yourself questions throughout the book will help you to think about what you
are studying while the Activities give you the chance to apply what you have
learnt in a range of modern contexts. At the end of each topic you will find
exam-style Review questions to help you check your progress.
Student support for this book can be found on the Dynamic Learning
Student website which contains an interactive copy of the book. Students can
access a range of free digital resources by visiting www.dynamic-learning-
student.co.uk and using the code printed on the final page of this
ebook to gain access to relevant resources. These free digital resources include:
G Data tables, for use when answering questions
G Tutorials, which work through selected problems and concepts using a
voiceover and animated diagrams
G Practical guidance to support experimental and investigative skills.

All diagrams and photographs can be launched and enlarged. There are also
Learning outcomes available at the beginning of every topic, and answer files
to all Test yourself and Activity questions. Extension questions, covering
some ideas in greater depth, are available at the end of each topic. The
Student Online icon, shown on the left, indicates where a resource such as a
Data Sheet, Tutorial, Practical Guidance or Extension questions is provided
on the Dynamic Learning Student website. All resources can be saved to your
local hard drive.
With the powerful Search tool, key words can be found in an instant,
leading you to the relevant page or alternatively to resources associated with
each key word.
Acknowledgements
We are grateful to John Apsey, Senior Examiner with Edexcel, for reading and
commenting on drafts of the book and CD-ROM resources. We would also
like to acknowledge the suggestions from teachers who commented on our
initial plans: Ian Davis, Neil Dixon and Tim Joliffe.
The team at Hodder Education, led by Gillian Lindsey, has made an
extremely valuable contribution to the development of the book and the CD-
ROM resources. In particular, we would like to thank Anne Trevillion, Anne
Wanjie, Deborah Sanderson, Anne Russell, Marion Edsall and Tony
Clappison for their skilful work on the print and electronic resources.
Graham Hill and Andrew Hunt

iv
A Note for Teachers
Edexcel Chemistry for AS Network disc
The Edexcel Chemistry for AS Network disc which accompanies the Student’s
Book and Dynamic Learning Student website provides a complete bank of
resources for teachers and technicians following the Edexcel specification.
Powered by Dynamic Learning, the Network disc contains the same
interactive version of the Student’s Book that is available on the Dynamic
Learning Student website, plus every resource that teachers might wish to use
in activities, discussions, practical work and assessment.
These additional resources on the Network disc include:
G a synoptic Topic overview for each of the nineteen topics showing how the
text and resources cover and follow the Edexcel specification, including
coverage of ‘How Science Works’. These synopses also indicate how the
resources on the Network disc can be used to create a teaching programme
and lesson plans
G Introductory PowerPoints for each topic
G Practical worksheets for students covering the entire course
G Teacher’s and technician’s notes for all practicals showing the intentions of
each practical, a suggested approach to it, health and safety considerations,
the materials and apparatus required by each group and answers to the
questions on the worksheets
G additional Weblinks
G additional Activities involving data analysis, application and evaluation
G 3D Rotatable models of molecules of interest
G answers to all Review questions in the Student’s Book, as well as answers to
all Extension questions available to students from the Dynamic Learning
Student website and to questions in the additional Activities on the
Network disc
G Interactive objective tests for each topic with answers.
All these resources are launched from interactive pages of the Student’s Book
on the Network disc. Teachers can also search for resources by resource type
or key words to allow greater flexibility in using the resource material.
A Lesson Builder allows teachers to build lessons by dragging and dropping
resources they want to use into a lesson group that can be saved and launched
later from a single screen.
The tools provided also enable teachers to import their own resources and
weblinks into the lesson group and to populate a VLE at the click of a button.
Risk assessment
As a service to users, a risk assessment for this text and associated resources
has been carried out by CLEAPSS and is available on request to the
Publishers. However, the Publishers accept no legal responsibility on any issue
arising from this risk assessment; whilst every effort has been made to check
the instructions for practical work in this book and associated resources, it is
still the duty and legal obligation of schools to carry out their own risk
assessment.

v
This page intentionally left blank
Unit 1

The Core Principles

of Chemistry
1 Chemical quantities
2 Energetics
3 Atomic and electronic
structure
4 Bonding and structure
5 Introduction to organic
chemistry
6 Hydrocarbons: alkanes
and alkenes
 1 Chemical quantities
Modern chemistry began when scientists understood the difference
between elements and compounds. Soon afterwards, chemists were
able to explain chemical changes in terms of atoms and molecules
and write chemical formulae. This led to the use of chemical
equations and experiments to determine the quantities of chemicals
which react and which are produced in chemical reactions.

1.1 Why study chemistry?

Chemistry is one of the sciences which helps us to develop our knowledge,
and to understand ourselves and all the materials and living things in the
Universe.
Some of the reasons for studying chemistry are outlined below. How well do
these reasons match your own expectations as you start this advanced
chemistry course?

Looking for patterns in chemical behaviour

Part of being a chemist involves getting a feel for the way in which chemicals
behave. Chemists get to know chemicals just as people get to know their
friends and family. They look for patterns in behaviour and recognise that
some of the patterns are familiar. For example, the elements sodium and
potassium are both soft and stored under oil because they react so readily with
air and water; copper sulfate is blue, like other copper compounds. By
understanding patterns, chemists can identify and make plastics like polythene
and medicines like aspirin.

Figure 1.1 씰
Aspirin is probably the commonest
medicine we use. The bark of willow
trees was used to ease pain for more
than 2000 years. Early in the twentieth
century, chemists extracted the active
ingredient from willow bark. Their
understanding of patterns in the
behaviour of similar compounds enabled
them to synthesise aspirin.

Working out the composition and structure of materials

New materials exist only because chemists understand how atoms, ions and
molecules are arranged in different materials and the forces which hold these
particles together. Thanks to this knowledge, we can enjoy fibres that breathe
but are waterproof, plastic ropes that are 20 times stronger than similar ropes
of steel (Figure 1.2) and metal alloys which can remember their shape.
Understanding the structure and bonding of materials is a central theme in
2 modern chemistry.
 Why study chemistry?

Controlling chemical changes

Four simple questions are at the heart of most chemical investigations.
G How much? – how much of the reactants do we need to make a product and
how much of the product will we produce?
G How fast? – how can we make sure that a reaction goes at the right speed:
not too fast and not too slow? How can we control the speed of reactions?
G How far? – will the chemicals we use react completely and make the
product, or will the reaction stop before we get all we want? If it does, what
can we do to get as big a yield as possible?
G How do reactions occur? – which bonds between atoms are breaking and
which new bonds are forming during a reaction?

Developing new skills

Chemistry involves doing things as well as gaining knowledge and Figure 1.2 쑿
understanding about materials. Chemists use their thinking skills and practical Plastic ropes made of polymers twenty
skills to solve practical problems. One of the frontiers of today’s chemistry times stronger than steel have made rock
involves nanotechnology, in which chemists work with particles as small as and ice climbing safer and easier.
individual atoms (Figure 1.3).
Increasingly, chemists rely on modern instruments to explore structures and
chemical changes. They also use information technology to store data, search
for information and to publish their findings.

Recognising the value of chemistry to society

Chemists study materials and try to change raw materials into more useful
substances. On a large scale, the chemical industry converts raw materials
from the earth, the sea and the air into valuable new products for society. A
Figure 1.3 쑿
good example of this is the Haber process, which turns natural gas and air into In the 1990s, two scientists working for
ammonia – the chemical used to make fertilisers, dyes and explosives. IBM cooled a nickel surface to ⫺269 ⬚C
A vital task for chemists is to analyse materials and find out what they are made in a vacuum chamber. Then they
of. When chemists have analysed a substance, they use symbols and formulae to introduced a tiny amount of xenon so
show the elements it contains. Symbols are used to represent the atoms in that some of the xenon atoms stuck to
elements; formulae are used to represent the ions and molecules in compounds. the nickel surface. Using a special
Analysis is involved in checking that our drinking water is pure and our food is safe instrument called a scanning tunnelling
to eat. People worry about pollution of the environment, but without chemical microscope, the scientists were able to
analysis we would not understand the causes or the scale of this pollution. move individual xenon atoms around on
the nickel surface and construct the IBM
Linking theories and experiments logo. Each blue blob is the image of a
single xenon atom.
Scientists test their theories by doing experiments. In chemistry, experiments
often begin with careful observation of what happens as chemicals react and
change. Theories are more likely to be accepted if predictions made from
them turn out to be correct when tested by experiment. Definitions
One of the reasons why Mendeléev’s periodic table was so successful was
because his predictions about the properties of missing elements turned out to Elements are the simplest
chemicals – they cannot be broken
be so accurate (Table 1.1).
down into simpler chemicals.
Compounds are chemicals
Mendeléev’s predictions in 1871 Actual properties in 1886
containing two or more elements
chemically combined together.
Grey metal Pale grey metal An atom is the smallest particle of an
Density 5.5 g cm⫺3 Density 5.35 g cm⫺3 element.
Relative atomic mass 73.4 Relative atomic mass 72.6
A molecule is a particle containing
Melting point 800 ⬚C Melting point 937 ⬚C
two or more atoms joined together
Formula of oxide GeO2 Ge forms GeO2 chemically.
An ion is an atom, or a group of
atoms, which has become electrically
Table 1.1 쑿 charged by the loss or gain of one or
Mendeléev’s predictions for germanium in 1871 and the properties it was found to more electrons.
have after its discovery in 1886 3
 Chemical quantities

Studying chemistry is more than about ‘what we know’ – it is also about ‘how
we know’. For example, the study of atomic structure has provided evidence
about the nature and properties of electrons, and this has led to an
explanation of the properties of elements and the patterns in the periodic
table in terms of the electron structures of atoms.

Learning to enjoy and take an interest in chemistry

As a schoolgirl, Dorothy Hodgkin became intensely interested in crystals and
their structures. In 1964, she won a Nobel Prize for her use of X-rays to
determine the structures of complex molecules such as penicillin and vitamin
B12. In 1996, Harry Kroto shared the Nobel Chemistry Prize for his part in
the discovery of a new form of carbon called ‘buckyballs’. According to Sir
Harry, ‘science is to do with fun and solving puzzles.’

Figure 1.4 쑿
This scientist is using a machine which
uses liquid chromatography followed by
mass spectrometry to research anti-
cancer (chemotherapy) drugs.

Definitions
Symbols are used to represent
elements, e.g. Fe for iron and C for
carbon.
Formulae are used to represent
compounds, e.g. H2O for water and
NaCl for sodium chloride.
A molecular formula shows the
numbers of atoms of the different
elements in one molecule of a
compound, e.g. CH4 for methane and
C2H6 for ethane.
An empirical formula shows the
simplest whole number ratio of the Figure 1.5 쑿
atoms of different elements in a Professor Harry Kroto with models of his buckyballs
compound, e.g. CH4 for methane and
CH3 for ethane.
The practical side of chemistry can really inspire some people. They get
pleasure from working with chemicals, producing high yields of products and
obtaining accurate results. Others are fascinated by the theory of chemistry
and the use of models to explain how materials react and change. Yet others
are interested in chemistry because of the ways in which it can improve our
lives – especially in medicine, nutrition, pharmacy, dentistry and the science
of materials.

1 Remind yourself of some patterns in the ways that chemicals behave.
Figure 1.6 쑿
A computer model of a C60 buckyball –
60 carbon atoms arranged like a cage
Test yourself
a) What happens when a more reactive metal (such as zinc) is added to a
solution in water of a compound of a less reactive metal (such as copper
sulfate)?
b) What forms at the negative electrode (cathode) during the electrolysis of a
metal compound?
c) What happens on adding an acid (such as hydrochloric acid) to a carbonate
(such as calcium carbonate)?
d) What do sodium chloride, sodium bromide and sodium iodide look like?

4
 From elements to compounds

2 This question concerns the substances ice, salt, sugar, copper, steel and limestone.
Which of these substances contain:
a) uncombined atoms
b) ions
c) molecules?
3 The structure of the main constituent in antifreeze is:
H H

H C C H

OH OH
What is:
a) its molecular formula
b) its empirical formula?

1.2 From elements to compounds

Compounds form when two or more elements combine. Apart from the atoms
of helium and neon, all atoms combine with other atoms.

Compounds of non-metals with non-metals

Water, carbon dioxide, methane in natural gas, sugar and ethanol (‘alcohol’)
are examples of compounds of two or more non-metals. Most of these non-
metal compounds melt and vaporise easily. They may be gases, liquids or
solids at room temperature and they do not conduct electricity.
In these compounds of non-metals, the atoms combine in small groups to
form molecules. For example, methane contains one carbon atom bonded to
four hydrogen atoms. The formula of the molecule is CH4. Figure 1.7 shows
three ways of representing a methane molecule. Models like that in the first
diagram represent atoms as little spheres.

H C H CH 4

H
Figure 1.7 쑿
Ways of representing a molecule of methane

It is possible to work out the formula of most non-metal compounds if you

know how many bonds the atoms normally form (Table 1.2).
Water is a compound of oxygen and hydrogen. Oxygen atoms form two
bonds and hydrogen atoms form one bond – so two hydrogen atoms can bond
to one oxygen atom (Figure 1.8) and the formula of water is H2O.

Element Symbol Number of bonds Colour in

formed molecular models
Carbon C 4 Black
Nitrogen N 3 Blue
Oxygen O 2 Red
Sulfur S 2 Yellow
Hydrogen H 1 White
O
Chlorine Cl 1 Green H H H 2O
Table 1.2 쑿 Figure 1.8 쑿
Symbols, number of bonds and colour codes of some non-metals Ways of representing a molecule of water
5
 Chemical quantities

There are double and even triple bonds between the atoms in some non-metal
compounds (Figure 1.9). Notice also that there is a strict colour code for the
atoms of different elements in molecular models – these colours are shown in
O C O
Table 1.2.
Figure 1.9 쑿 In practice, it is not possible to predict the formulae of all non-metal
Bonding in carbon dioxide showing the compounds. For example, the bonding rules in Table 1.2 cannot account for
double bonds between atoms the formulae of carbon monoxide, CO, or sulfur dioxide, SO2.

Test yourself
4 Draw the various ways – like those for methane in Figure 1.7 – of representing
the following compounds:
a) hydrogen chloride
b) carbon disulfide.
5 Name the elements present and work out the formula of the following
compounds:
a) hydrogen sulfide
b) dichlorine oxide
c) hydrogen nitride (ammonia).

Compounds of metals with non-metals

Common salt (sodium chloride), limestone (calcium carbonate) and copper
sulfate are all examples of compounds of metals with non-metals. These
metal/non-metal compounds melt at much higher temperatures than
compounds of non-metals – they are solids at room temperature. They conduct
electricity as molten liquids but not as solids. Metal/non-metal compounds
conduct electricity as liquids because they consist of ions. For example, sodium
chloride consists of sodium ions, Na⫹, and chloride ions, Cl⫺.
The formula of sodium chloride is NaCl (or Na⫹Cl⫺) because the positive
charge on one Na⫹ ion is balanced by the negative charge on one Cl⫺ ion. In
a crystal of sodium chloride there are equal numbers of sodium ions and
chloride ions (Figure 1.10).
The formulae of all metal/non-metal (ionic) compounds can be worked out
by balancing the charges on positive and negative ions. For example, the
formula of potassium oxide is K2O (or (K⫹)2O2⫺). Here, two K⫹ ions balance
the charge on one O2⫺ ion.
Elements such as iron, which have two different ions (Fe2⫹ and Fe3⫹), have
two sets of compounds – iron(II) compounds such as iron(II) chloride, FeCl2,
and iron(III) compounds such as iron(III) chloride, FeCl3.
Table 1.3 shows the names and formulae of some ionic compounds. Notice
that the formula of magnesium nitrate is Mg(NO3)2 (or Mg2⫹(NO3⫺)2). The
brackets round NO3⫺ show that it is a single unit containing one nitrogen and

Figure 1.10 씰
A space-filling model
and a ball-and-stick
model showing the
structure of sodium
chloride Na+

Cl–

6
space-filling model ball-and-stick model
 Writing chemical equations

three oxygen atoms bonded together with a 1⫺ charge. Other ions, like OH⫺,
SO42⫺ and CO32⫺, must also be treated as single units and put in brackets
when there are two or three of them in a formula.

Name of compound Formula

Magnesium nitrate Mg2⫹(NO3⫺)2, Mg(NO3)2 Data

Aluminium hydroxide Al3⫹(OH⫺)3, Al(OH)3

Zinc bromide Zn2⫹(Br⫺)2, ZnBr2

Lead nitrate Pb2⫹(NO3⫺)2, Pb(NO3)2

Calcium iodide Ca2⫹(I⫺)2, CaI2

Copper(II) carbonate Cu2⫹CO32⫺, CuCO3

Silver sulfate (Ag⫹)2SO42⫺, Ag2SO4

Table 1.3 쑿
The names and formulae of some ionic compounds

Test yourself
6 The formula of aluminium hydroxide must be written as Al(OH)3. Why is AlOH3
wrong?
7 Write the formulae of the following ionic compounds:
a) potassium sulfate
b) aluminium oxide
Data
c) lead carbonate
d) zinc hydroxide
e) iron(III) sulfate
8 Which of the following compounds consist of molecules and which consist of
ions?
a) octane (C8H18) in petrol
b) copper(I) oxide
c) pure sulfuric acid
d) lithium fluoride
e) phosphorus trichloride
9 Compare non-metal (molecular) compounds with metal/non-metal (ionic)
compounds in
a) melting temperatures and boiling temperatures
b) conduction of electricity as liquids.

1.3 Writing chemical equations

Burning and rusting are good examples of chemical reactions. When they
occur, chemical bonds in the reactants break and then new bonds form in the
products. The photo in Figure 1.11 shows sparks from a sparkler – these sparks
are bits of burning magnesium. When magnesium burns in air, it reacts with
oxygen to form white magnesium oxide. A word equation for the reaction is:
magnesium ⫹ oxygen → magnesium oxide

Balanced chemical equations

When chemists write equations, they use symbols and formulae rather than
words. However, writing a word equation is a useful first step towards getting a Figure 1.11 쑿
balanced chemical equation with symbols. There are four key steps in writing When sparklers burn, bits of magnesium
7
an equation. react with oxygen in the air.
 Chemical quantities
Definition
A balanced chemical equation
describes a chemical reaction using
symbols for the reactants and
products. The numbers of each kind
of atom are the same on both sides of
the equation.
Figure 1.12 씰
Figure 1.13 쑿
When methane (natural gas) burns on a
hob, it reacts with oxygen in the air to
8 form carbon dioxide and water.
Step 1: Write a word equation for the reaction.
magnesium ⫹ oxygen → magnesium oxide
Step 2: Write symbols for the elements and formulae for the compounds in
the word equation.
Mg ⫹ O2 → MgO
Remember that oxygen, hydrogen, nitrogen and the halogens are
diatomic molecules with two atoms in their molecules – so they are
written as O2, H2, N2, F2, Cl2, Br2 and I2. All other elements are shown
as single atoms.
Step 3: Balance the equation by putting numbers in front of the symbols and
formulae, so that the numbers of each type of atom are the same on
both sides of the equation.
2Mg ⫹ O2 → 2MgO
Never change a formula to make an equation balance. The formula of
magnesium oxide is always MgO and never MgO2 or Mg2O; or
anything else for that matter.
Step 4: Add state symbols to show the state of each substance in the equation.
Use (s) for solid, (l) for liquid, (g) for gas and (aq) for an aqueous
solution (a substance dissolved in water).
2Mg(s) ⫹ O2(g) → 2MgO(s)
Balanced chemical equations are more useful than word equations because
they show:
G the symbols and formulae of the reactants and products
G the relative numbers of atoms and molecules in the reaction.
Modelling equations
Chemists often use models to understand what is happening to the different
atoms, molecules and ions during a reaction. Figure 1.12 shows how molecular
models can give a picture of the reaction between hydrogen and oxygen at an
atomic level.
2H2O
2H2 O2
two hydrogen one oxygen
two water
molecules
molecules molecule
Using molecular models like those in Figure 1.12, it is possible to see which
bonds break in the reactants and which new bonds form in the products. The
models also confirm that the atoms have simply been rearranged during the
reaction, as there are exactly the same atoms on both sides of the equation.
Test yourself
10 a) Use molecular models to show what happens when methane burns in
oxygen (Figure 1.13).
b) Draw a diagram for this reaction, similar to that shown in Figure 1.12.
 Types of chemical change

11 Write balanced equations for the following word equations:

a) sodium ⫹ oxygen → sodium oxide
b) sodium oxide ⫹ water → sodium hydroxide Data
c) hydrogen ⫹ chlorine → hydrogen chloride
d) zinc ⫹ hydrochloric acid (HCl) → zinc chloride ⫹ hydrogen
e) methane (CH4) ⫹ oxygen → carbon dioxide ⫹ water
f) iron ⫹ chlorine → iron(III) chloride.

1.4 Types of chemical change

Chemists classify chemical reactions in order to make sense of the thousands
of reactions which they study. By putting similar reactions into groups or sets,
chemists can predict how different substances will behave.

Thermal decomposition Note

Calcium carbonate breaks up (decomposes) on heating to form calcium oxide The decomposition of calcium
and carbon dioxide (Figure 1.14): carbonate (limestone) to calcium oxide
CaCO3(s) → CaO(s) ⫹ CO2(g) (quicklime) is important for agriculture
and industry. Quicklime is used to
This is an example of thermal decomposition. Calcium carbonate is stable at neutralise acid soils and it also reacts
room temperature, but it becomes unstable when heated with a hot Bunsen with water to make calcium hydroxide
flame. (slaked lime), which is an important
Other metal carbonates, except those of group 1 metals, also decompose on industrial alkali.
heating. Carbonates of metals below copper in the reactivity series are so
unstable that they cannot exist at room temperature.

Figure 1.14 쑿
Quicklime is used to neutralise acid soils, making them more fertile.

Hydrated compounds like hydrated copper sulfate, CuSO4.5H2O, which Definition

contain water as part of their structure, also decompose on heating. Fairly Thermal decomposition is the
gentle heating causes most hydrates to give off water vapour which often breaking up of substances into
condenses to water on the cooler parts of the apparatus. simpler substances by heating.

heat
CuSO4.5H2O(s) → CuSO4(s) ⫹ 5H2O(g)
blue hydrated white anhydrous
copper sulfate copper sulfate 9
 Chemical quantities
Figure 1.15 쑿
This statue is made from limestone
(calcium carbonate). Its worn and pitted
appearance has been caused over many
years by the action of acids in ‘acid rain’.
Definition
Spectator ions are ions which take
no part in a reaction.
10
Reactions of acids
Acids are compounds with characteristic properties:
G they form solutions in water with a pH below 7
G they change the colour of indicators
G they react with metals above hydrogen in the reactivity series forming
hydrogen plus an ionic metal compound called a salt
Mg(s) ⫹ 2HCl(aq) → MgCl2(aq) ⫹ H2(g)
G they react with metal oxides and metal hydroxides to form salts and water
CuO(s) ⫹ H2SO4(aq) → CuSO4(aq) ⫹ H2O(l)
G they react with carbonates to form salts, carbon dioxide and water
(Figure 1.15)
CaCO3(s) ⫹ 2HCl(aq) → CaCl2(aq) ⫹ CO2(g) ⫹ H2O(l)
What makes an acid an acid?
Acids do not simply mix with water when they dissolve in it – they react with
it to produce aqueous hydrogen ions, H⫹(aq).
water
HCl(g) → H⫹(aq) ⫹ Cl⫺(aq)
All acids produce H⫹(aq) ions with water and this is why they all react in a
similar way. The typical reactions of dilute acids in water are the reactions of
aqueous hydrogen ions. So, we can rewrite the equations for acids showing the
ions in acids and in metal/non-metal (ionic) compounds.
With metals
Mg(s) ⫹ 2H⫹(aq) ⫹ 2Cl⫺(aq) → Mg2⫹(aq) ⫹ 2Cl⫺(aq) ⫹ H2(g)
Notice that the chloride ions are the same before and after the reaction –
because of this they are called spectator ions. For clarity, chemists often omit
spectator ions from ionic equations like the one above. So, the equation
becomes:
Mg(s) ⫹ 2H⫹(aq) → Mg2⫹(aq) ⫹ H2(g)
With metal oxides and hydroxides
Cu2⫹O2⫺(s) ⫹ 2H⫹(aq) ⫹ SO42⫺(aq) → Cu2⫹(aq) ⫹ SO42⫺(aq) ⫹ H2O(l)
This time, the Cu2⫹ and SO42⫺ ions take no part in the reaction. So, we can
simplify the equation to:
O2⫺(s) ⫹ 2H⫹(aq) → H2O(l)
With carbonates
Ca2⫹CO32⫺(s) ⫹ 2H⫹(aq) ⫹ 2Cl⫺
→ Ca2⫹(aq) ⫹ 2Cl⫺(aq) ⫹ CO2(g) ⫹ H2O(l)
In this case, the Ca2⫹ and 2Cl⫺ are spectator ions, so the equation becomes:
CO32⫺ (s) ⫹ 2H⫹(aq) → CO2(g) ⫹ H2O(l)
Reactions of bases and alkalis
Bases are ‘anti-acids’ – they are the chemical opposites of acids. Acids donate
(give up) hydrogen ions; bases (such as oxides, hydroxides and carbonates)
accept hydrogen ions.
Alkalis are bases which dissolve in water. The common laboratory alkalis
are sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia.
Alkalis form solutions with a pH above 7, so they change the colours of
acid–base indicators.
 Chemical quantities

Gas volume calculations

Gas volume calculations are straightforward when all the relevant substances
are gases. In these cases, the ratio of the gas volumes in the reaction is the
same as the ratio of the numbers of moles in the equation.

Worked example
What volume of oxygen reacts with 60 cm3 methane and what volume of
carbon dioxide is produced if all volumes are measured at the same
temperature and pressure?
Answer
The equation for the reaction is:
CH4(g) ⫹ 2O2(g) → CO2(g) ⫹ 2H2O(l)
1 mol 2 mol 1 mol insignificant volume
∴ 1 volume 2 volumes 1 volume of liquid below 100 ⬚C
So, 60 cm3 methane reacts with 120 cm3 oxygen to produce 60 cm3 carbon
dioxide.

By measuring the volumes of gases involved in reactions, and then converting

these volumes to amounts of gas in moles, it is possible to deduce equations
Practical
for reactions. This is illustrated in the activity on page 23.
guidance

Test yourself
30 Assuming that all gas volumes are measured under the same conditions of
temperature and pressure, what volume of:
a) nitrogen forms when 2 dm3 ammonia, NH3, decomposes into its elements
b) oxygen is needed to react with 50 cm3 ethane, C2H6, when it burns, and
what volume of carbon dioxide forms?
31 a) Copy and balance this equation for the complete combustion of propane
(Calor gas)
C3H8(g) ⫹ ______ O2(g) → ______ CO2(g) ⫹ ______ H2O(g)
b) What volume of oxygen reacts with 200 cm3 of propane and what volume of
carbon dioxide is produced? (Assume that all volumes are measured at
room temperature and pressure.)
c) What is the mass of the carbon dioxide produced?
32 What volume of gas forms at room temperature and pressure when:
a) 0.654 g of zinc reacts with excess dilute hydrochloric acid
b) 2.022 g of potassium nitrate, KNO3, decomposes on heating to potassium
nitrite, KNO2, and oxygen?

Calculating the concentration of solutions

The concentration of a solution tells us how much solute is dissolved in a
certain volume of solution. It is usually measured in grams per cubic decimetre
(g dm⫺3) or moles per cubic decimetre (mol dm⫺3). For example, a solution of
sodium hydroxide containing 1.0 mol dm⫺3 has 1 mole of sodium hydroxide
(40 g of NaOH) in 1 dm3 (1000 cm3) of solution. Figure 1.25 shows how to
prepare a solution with a specified concentration.

22
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and subsequently enlarges it by additions from its own body. The
beautiful Insects of the genus Cryptocephalus, which is fairly well
represented in Britain, belong to this division. The exotic group
Megalopodes is incorrectly placed in Camptosomes; the side pieces
of the prothorax meet in it behind the middle coxae, as they do in
Rhynchophora. The species of Megalopodes stridulate by means of
an area on the base of the meso-scutellum rubbed by a ridge inside
the pronotum, as in the Cerambycidæ.

iii. The division Cyclica includes the great majority of Chryomelidae;

we have not less than 170 species in Britain. The larvae live, like
those of Lepidoptera, at the expense of foliage, and the species
frequently multiply to such an extent as to be injurious. Some of
them are destroyed in great numbers by Hymenopterous parasites,
the Braconid genus Perilitus being one of the best known of these; in
some cases the parasite deposits its eggs in either the larva or
perfect Insect of the beetle, and the metamorphoses of the parasites
in the latter case are sometimes, if not usually, completed, the larvae
emerging from the living beetles for pupation.

iv. The Cryptostomes, though comparatively few in number of

species, include some very remarkable beetles. There are two
groups, Hispides and Cassidides. The former are almost peculiar to
the tropics and are not represented by any species in the British
fauna. The head in this group is not concealed; but in the Cassidides
the margins of the upper surface are more or less expanded, so that
the head is usually completely hidden by the expansion of the
pronotum. Both the groups are characterised by the antennae being
inserted very near together, and by the short claw-joint of the feet.
Hispa is one of the most extensive of the numerous genera of
Hispides, and is remarkable from the imago being covered on the
surface with long, sharp spines. But little is known as to the
metamorphosis, beyond the fact already alluded to, that the larvae of
several species mine the interior of leaves. The larva of Hispa
testacea, according to Perris,[147] makes use of the leaves of Cistus
salvifolius in Southern Europe; it is broad and flat, and possessed of
six short legs. The eggs are not deposited by the parents inside the
leaves, but are probably attached to various parts of the plant. After
hatching, the young larva enters a leaf, and feeds on the
parenchyma without rupturing the epidermis; but when it has
consumed about three-fourths of the soft interior of the leaf it
ruptures the epidermis of the upper surface, and seeks another leaf;
this found, it places itself on the midrib, tears the upper epidermis,
and lodges itself in the leaf. In the case of this second leaf it attacks
the parenchyma in the neighbourhood of the petiole, and so forms
an irregular tube which has an open mouth, the point of entry. In this
tube it undergoes its metamorphosis. Each larva, it is said, always
makes use of two leaves, and of two opposed leaves. A knowledge
of the habits of some of the larger of the exotic Hispides would be of
much interest.

Fig. 144—Pupa of Cassidid beetle (? Aspidomorpha sp.). A, With

appendage extended; B, with the appendage reposing on the
back. New Britain.

The Cassidides, in addition to the curious marginal expansion of

their upper surface, have the power of withdrawing the head into the
thorax, and hence they are often called shield or tortoise-beetles.
They exhibit considerable variety in form and colour, and some of
them display a peculiar metallic reflection of great delicacy and
beauty; this disappears entirely after death, but it may be restored by
thoroughly moistening the dead Insect. The colour, therefore,
probably depends on the presence of water in the integument. The
larvae of Cassidides are notorious on account of their habit of
covering their bodies with dried excrement, for which purpose they
are provided with a forked process at the posterior extremity; this
serves to place the protecting matter in a proper position and to
retain it there. The excrement assumes in various species forms so
peculiar that they cannot be considered merely incidental. In several
species this covering-matter is like lichen. This is the case with
Dolichotoma palmarum, the larva of which has, in place of the usual
fork, a more complex appendage on the back for the purpose of
preparing and retaining its peculiar costume. The pupae, too,
sometimes retain the larval skin. An extremely remarkable pupa of a
Cassidid—possibly of the genus Aspidomorpha—was recently found
by Dr. Arthur Willey in New Britain (Fig. 144). The back of the pupa is
covered with a complex appendage, so that the creature has no
resemblance to an Insect; this appendage is perhaps capable of
being moved, or even extended (Fig. 144, A), during life. Whether it
may be formed by the retention of portions of the moulted skins of
the larva we cannot say with certainty.

Fig. 145—Nest of intestinally-made filaments under which the larva of

Porphyraspis tristis lives.

The most remarkable of the Cassidid coverings yet discovered are

those formed by certain small beetles of the tropical American genus
Porphyraspis. P. tristis is apparently a common Insect at Bahia,
where it lives on a cocoa-palm. The larva is short and broad, and
completely covers itself with a very dense coat of fibres, each many
times the length of the body, and elaborately curved so as to form a
round nest under which the larva lives. On examination it is found
that these long threads are all attached to the anal extremity of the
Insect, and there seems no alternative to believing that each thread
is formed by small pieces of fibre that have passed through the
alimentary canal, and are subsequently stuck together, end to end.
The process of forming these long fibres, each one from scores of
pieces of excrement, and giving them the appropriate curve, is truly
remarkable. The fibres nearest to the body of the larva are abruptly
curled so as to fit exactly, and make an even surface; but the outside
fibres stand out in a somewhat bushy fashion. The construction is
much like that of a tiny bird's nest. Señor Lacerda informed the writer
that the larva makes a nest as soon as it is hatched. Another
Porphyraspis—P. palmarum—has been recorded as forming similar
nests on a species of Thrinax in St. Domingo. Candèze says[148]
that when it has completed its growth the larva ejects on to the leaf a
quantity of semi-liquid matter, and this, on drying, sticks the nest to
the leaf, so that the metamorphosis is effected under shelter.

Fam. 79. Cerambycidae (Longicorns).—Form usually oblong, not

much curved in outline at the sides; surface very frequently rendered
dull by a very minute hairiness, which often forms a pattern;
antennae usually long, and their insertion much embraced by the
eyes. This great family of beetles includes some 12,000 or 13,000
known species. The elegance and variety of their forms and the
charm of their colours have caused them to attract much attention,
so that it is probable that a larger proportion of the existing species
have been obtained than is the case in any other of the great
families of Coleoptera. Still it is not likely that one-half of the living
forms are known. It is not possible at present to point out any one
character of importance to distinguish Cerambycidae from
Chrysomelidae, though the members of the two families have, as a
rule, but little resemblance in external appearance. Most of them live
on, or in, wood, though many are nourished in the stems of
herbaceous plants. The larvae live a life of concealment, and are
soft, whitish grubs with powerful mandibles, and usually with a
comparatively small head, which is not much exserted from the
thorax. Most of them are without legs, but a good many have three
pairs of small legs, and there are numerous cases in which the
surface of the body is furnished above or below with swellings
believed to act as pseudopods (Fig. 84), and help the larvae to move
about in their galleries; but this is probably not the sole function of
these organs, as their surface is varied in character, and often not of
a kind that appears specially adapted to assist in locomotion. There
is a slight general resemblance between the larvae of Cerambycidae
and those of Buprestidae, and when the thorax of a Longicorn larva
is unusually broad, e.g. Astynomus, this similarity is very
pronounced.

Fig. 146—Saperda populnea. Britain.

The modes of life of Cerambycid larvae exhibit considerable variety,

and much perfection of instinct is displayed by the larvae, as well as
by the mother beetles. The larvae of Saperda populnea, are
common in certain woods in the South of England in the stems of
aspen; they consume only a small quantity of the interior of the stem,
and are probably nourished by an afflux of sap to the spot where
they are situated. Elaphidion villosum is called the oak-pruner in
North America. The parent beetle lays an egg near the axilla of a
leaf-stalk or small stem, and the young larva enters this and feeds on
the tender material; as it grows it enters a larger limb, and makes an
incision within this in such a manner that the wood falls to the ground
with the larva within it, the dead wood serving subsequently as
pabulum and as a shelter, within which the metamorphosis is
completed. The species of the American genus Oncideres are called
girdlers, because the parent beetle, after laying an egg in a small
branch, girdles this round with a deep incision, so that the portion
containing the larva sooner or later falls to the ground. The growth of
a Longicorn larva frequently takes more than a year, and under
certain circumstances it may be enormously prolonged.
Monohammus confusus has been known to issue from wooden
furniture in a dwelling-house when the furniture was fifteen years old.
Individuals of another Longicorn have issued from the wood of a
table, twenty and even twenty-eight years after the felling of the tree
from which the furniture was made. Sereno Watson has related a
case from which it appears probable that the life of a Longicorn
beetle extended over at least forty-five years.[149] It is generally
assumed that the prolongation of life in these cases is due to the
beetle resting quiescent for long after it has completed the
metamorphosis. Recent knowledge, however, renders it more
probable that it is the larval life that is prolonged; the larva continuing
to feed, but gaining little or no nutriment from the dry wood in these
unnatural conditions. Mr. C. O. Waterhouse had for some years a
Longicorn larva under observation, feeding in this way in the wood of
a boot-tree;[150] the burrows in the wood contained a great deal of
minute dust indicating that the larva passed much matter through the
alimentary canal, probably with little result in the way of nutriment.

There are numerous Longicorns that bear a great resemblance in

form and colour to Insects to which they are not related.
Haensch[151] has noticed that species of the genus Odontocera
resemble various Hymenoptera, one species being called O.
braconoides; he also observed that these Hymenoptera-like
Longicorns, instead of withdrawing their underwings under the elytra
as beetles generally do, vibrate them rapidly like Hymenoptera. A
large number of Longicorns stridulate loudly by rubbing a ridge
inside the pronotum on a highly specialised, striate surface at the
base of the scutellum, and therefore covered up when the Insect is
contracted in repose. A few produce noise by rubbing the hind
femora against the edges of the elytra, somewhat after the fashion of
grasshoppers. In this case there appears to be comparatively little
speciality of structure, the femora bearing, however, more or less
distinct small granules. The species of the Hawaiian genus
Plagithmysus produce sound in both these manners, the thoracic
stridulating organ being beautifully developed, while in some species
the margin of the elytra and base of the femora are also well adapted
for the purpose of sound-production, and in a few species of the
genus there are also highly-developed stridulating surfaces on the
hind and middle coxae. This is the only case in which a beetle is
known to possess more than one set of sound-organs in the imago
state.

Three divisions of this family are distinguished, viz.—

 1. Front coxae large and transverse; prothorax with distinct side margins.
.......... Sub-fam. 1. Prionides.
2. Front coxae not greatly extended transversely, thorax not margined; last
joint of maxillary palpus not pointed, usually broader (more or less) than
the preceding joint. .......... Sub-fam. 2. Cerambycides.
3. Front coxae usually round and deeply embedded; last joint of maxillary
palpus pointed; front tibiae with a more or less distinct, slanting groove
on the inner side. .......... Sub-fam. 3. Lamiides.

The Prionides are on the average considerably larger in size than

the members of the other divisions, and they include some of the
largest of Insects. The Amazonian Titanus giganteus and the Fijian
Macrotoma heros are amongst the most gigantic. Some of the
Prionides have a great development of the mandibles in the male
sex analogous to that we have already noticed in Lucanidae. The
larvae of the large Prionides appear in various parts of the world to
have been a favourite food with native tribes, and Lumholz states
that they are really good eating. In consequence of the destruction of
forests that has progressed so largely of late years these gigantic
Prionides have become much rarer.

Several aberrant forms are included in Prionides. The genus

Parandra has five-jointed tarsi; the third joint being much smaller
than usual, so that the fourth joint is not concealed by it. The
Brazilian Hypocephalus armatus was for long a subject of dispute as
to its natural position, and was placed by different authorities in
widely-separated families of Coleoptera. The structure of this
aberrant Longicorn seems to be only explicable on the hypothesis of
warfare amongst the males.[152] Nothing is, however, known as to
the habits and history of the Insect, and only one or two specimens
of the female have yet been obtained.

The family Spondylidae has been proposed for some of these

aberrant Longicorns, but as it includes but very few, and highly
discrepant, species, it is neither natural nor of much use for
systematic purposes.
The Lamiides are the most highly specialised division of the
Longicorns, and includes the larger number of the species. The front
of the head is usually placed at right angles to the vertex, and in
some cases (groups Hippopsini, Spalacopsini) it is strongly inflexed,
so that the mouth is placed on the under side of the head. The
extension of the eyes round the antennae is accompanied by very
curious shapes of those organs, and not infrequently each eye is
divided into two more or less widely-separated parts, so that the
Insect has, on the external surface, four eyes.

Series VI. Rhynchophora.

Head more or less prolonged in front to form a snout or beak,

called rostrum. Tarsi four-jointed, usually at least the third joint
broad and densely pubescent beneath.

This enormous series includes about 25,000 species, and as may

well be imagined shows a great variety of structure amongst its
forms. The vast majority may, however, be readily recognised by the
two characters mentioned above. There are some cases in which the
beak is indistinct, and others in which the tarsi are five-jointed
(Dryophthorus), and even slender (Platypides). In these cases a
close examination shows that the gular region on the middle of the
back of the under surface of the head cannot be detected, and that
the back of the prosternum is very strongly consolidated by the side-
pieces of the thorax meeting together and being very firmly joined
behind the coxae. The beak is in the great majority perfectly distinct,
though it varies so extremely in form that it can only be briefly
described by saying that it is a prolongation of the head in front of
the eyes, or that the antennae are inserted on its sides near to, or far
from, the tip. It has been ascertained in many cases that the rostrum
is used by the female to assist in placing the eggs in suitable places,
a hole being bored with it; in some cases it is also used to push the
egg far into the hole in which it has previously been placed by the
ovipositor; but there are many forms in which it is fairly certain that it
is not so used. What purpose it serves in the male is totally
unknown. In many members of the series, the rostrum differs in form
in the two sexes, and in most, if not in all, these cases it is clear that
the distinctions tend in the direction of making the beak of the female
more efficient for the mechanical purpose we have mentioned.

Fig. 147.—Eugnoristus monachus ♀. Madagascar. A, The imago; B,

front of pronotum, head, and rostrum.

It was proposed by Leconte and Horn to separate this series from all
the other Coleoptera as a primary division, and they looked on it as
of lower or more imperfect structure. Packard has very properly
protested against this interpretation; and there seems to be no
reason whatever for considering the Rhynchophora as "lower" than
other beetles; indeed we should be inclined to place such forms as
Calandrides amongst the most perfect of Insects; their external
structure (as shown by Eugnoristus monachus, Fig. 147) being truly
admirable.

Only four families of Rhynchophora can be at present accepted as

satisfactory; one of these—Curculionidae—includes an enormous
majority of the whole series. Though it is probable that it will
ultimately be divided into several families, the attempts to that end
that have already been made are not satisfactory.
Fam. 80. Anthribidae.—Palpi usually not covered, but distinct and
flexible. Antennae often long, not elbowed, the first joint not very
long. Third joint of tarsus small, usually much concealed by being
embraced by the second joint. Pygidium exposed; propygidium
deeply grooved in the middle. This family includes 800 or more
species, which are mostly tropical; it is very sparsely represented in
the faunas of Europe and North America. It is quite distinct from
Curculionidae with which it was formerly associated. It contains
many graceful Insects having a certain resemblance with Longicorns
on account of the large development of the antennae. The habits
and metamorphoses are but little known. It seems probable that
many species find their nutriment in old wood or boleti The larvae of
some genera (Cratoparis and Araeocerus) have legs, but in others
the legs are wanting, and the larvae are said to completely resemble
those of Curculionidae. In the larva of our tiny British species,
Choragus sheppardi, the legs are replaced by three pairs of thoracic,
sac-like pseudopods. This Insect makes burrows in dead branches
of hawthorn. The larvae of the genus Brachytarsus have been
ascertained to prey on Coccidae.

Fig. 148—Platyrhinus latirostris, Anthribidae. Britain. A, the perfect

Insect; B, tarsus and tip of tibia.

Fam. 81. Curculionidae (Weevils).—The beak of very variable

length and thickness; the palpi small, nearly always concealed within
the mouth, short, and rigid. Labrum absent. Antennae of the majority
elbowed, i.e. with the basal joint longer, and so formed that when it is
laterally extended the other joints can be placed in a forward
direction. This enormous family includes about 20,000 known
species, and yet a large portion of the species yearly brought from
the tropics still prove to be new. The rostrum or beak exhibits
excessive variety in form, and is in many cases different in the
sexes; in this case it is usually longer and thinner in the female. As
the rostrum is one of the chief characters by which a member of the
family may be recognised, it is necessary to inform the student that
in certain forms (the Australian Amycterides, e.g.) the organ in
question may be so short and thick that it is almost absent. In these
cases the Insect may be identified as a Curculionid by the gular area
being absent on the under side of the head, and by the concealment
of the palpi. The tarsi are usually of the same nature as those of
Phytophaga, already described, but the true fourth joint is less
visible. In the Brachycerides this joint is not present, and the third
joint is not lobed. The palpi are flexible and more or less exserted in
a very few species (Rhynchitides); in Rhinomacerides there is also
present a minute labrum. The front coxae are deeply embedded, and
in many forms the prosternum is peculiar in structure; the side-
pieces (epimera) meeting at the back of the prosternum in the middle
line. This, however, is not universal in the family, and it occurs in
some other beetles (e.g., Megalopodides of the Phytophaga). The
larvae are without legs. They are vegetarian, the eggs being
deposited by the mother-beetle in the midst of the food. These larvae
may be distinguished from those of Longicorns by the general form,
which is sub-cylindric or rather convex, not flattened, and more
particularly by the free, exserted head, the mouth being directed
downwards; the attitude is generally a curve, and the anterior part of
the body is a little the thicker. No part of plants is exempt from the
attacks of the larvae of Curculionidae; buds, twigs, leaves, flowers,
fruits, bark, pith, roots and galls may each be the special food of
some Curculionid. Certain species of the sub-families Rhynchitides
and Attelabides prepare leaves in an elaborate manner to serve as
food and dwelling for their young. If young birches, or birch bushes
from 5 to 10 feet in height, be looked at in the summer, one may
often notice that some of the leaves are rolled so as to form, each
one, a little funnel. This is the work of Rhynchites (or Deporaus)
betulae, a little Curculionid beetle (Fig. 149). An inspection of one of
these funnels will show that it is very skilfully constructed.
 Fig. 149.—The leaf-rolling of Rhynchites betulae. Britain. A, Female
beetle, magnified; B, the beetle forming the first incision on a leaf;
C, the completed roll. (B and C after Debey.)

The whole of a leaf is not used in the formation of a funnel, cuts

being made across the leaf in suitable directions. The beetle
standing on a leaf, as shown in the figure, proceeds to cut with its
mandibles an incision shaped like an erect S, commencing at a
certain part of the circumference, and ending at the midrib of the
leaf; the beetle then goes to the other side of the midrib, and
continues its incision so as to form another S-like curve considerably
different from the first; being prostrate and less abrupt. Thus the
blade of the leaf is divided into two halves by certain curved
incisions, the midrib remaining intact. The little funnel-twister now
commences to roll up the leaf to form the funnel; and this part of the
work is greatly facilitated by the shape of the incisions. Going back to
the spot where it commenced work, by the aid of its legs it rolls one
side of the leaf round an ideal axis, somewhat on the same plan as
that adopted by a grocer in forming a paper-funnel for sugar. The
incisions are found to be just of the right shape to make the overlaps
in the rolling, and to retain them rolled-up with the least tendency to
spring back. After some other operations destined to facilitate
subsequent parts of its task, the beetle enters the rolled-up part of
the leaf and brings it more perfectly together; it again comes out and,
pursuing a different system, holds on with the legs of one side of the
body to the roll, and with the other legs drags to it the portion of the
leaf on the other side of the midrib so as to wrap this part (i.e. the
result of its second incision) round the part of the funnel already
constructed. This being done the Insect again enters the funnel,
bites three or four small cavities on the inside of the leafy wall and
deposits an egg in each. Afterwards it emerges and fits the overlaps
together in a more perfect manner so as to somewhat contract the
funnel and make it firmer; then proceeding to the tip, this is operated
on by another series of engineering processes and made to close
the orifice; this part of the operation being analogous to the closing
by the grocer of his paper-funnel after the sugar has been put in. The
operation of the beetle is, however, much more complex, for it
actually makes a sort of second small funnel of the tip of the leaf,
bends this in, and retains it by tucking in some little projections. The
work, which has probably lasted about an hour, being now
completed, the creature takes a longer or shorter rest before
commencing another funnel. We have given only a sketch of the
chief points of the work, omitting reference to smaller artifices of the
craft master; but we may remark that the curved incisions made by
the beetle have been examined by mathematicians and duly extolled
as being conducted on highly satisfactory mathematical principles. It
is impossible at present for us to form any conception as to the
beetle's conceptions in carrying out this complex set of operations.
Our perplexity is increased if we recollect its life-history, for we then
see that neither precept or example can have initiated its
proceedings, and that imitation is out of the question. The eggs
hatch in their dark place, giving rise to an eyeless maggot, which
ultimately leaves the funnel for the earth. The parts of this maggot
subsequently undergo complete change to produce the motionless
pupa of entirely different form, from which emerges the perfect
Insect. Hence the beetle cannot be considered to have ever seen a
funnel, and certainly has never witnessed the construction of one,
though, when disclosed, it almost immediately sets to work to make
funnels on the complex and perfect system we have so imperfectly
described. More general considerations only add to the perplexity we
must feel when reflecting on this subject. Why does the Insect
construct the funnel at all? As a matter of protection it appears to be
of little use, for the larvae are known to suffer from the attacks of
parasites as other Insects do. We have not the least reason for
supposing that this mode of life for a larva is, so far as utility is
concerned, better than a more simple and usual one. Indeed,
extraordinary as this may appear, it is well known that other species
of the same genus adopt a simple mode of life, laying their eggs in
young fruits or buds. We think it possible, however, that a knowledge
of the mode of feeding of this larva may show that a more perfect
nutrition is obtained from a well-constructed cylinder, and if so this
would to a slight extent satisfy our longing for explanation, though
throwing no light whatever on the physiology or psychology of the
artificer, and leaving us hopelessly perplexed as to why a beetle in
ages long gone by should or could adopt a mode of life that by long
processes of evolution should, after enormous difficulties have been
overcome, attain the perfection we admire.[153]

Fam. 82. Scolytidae.—Rostrum extremely short, broad; tibiae

frequently denticulate externally; antennae short, with a broad club.
This family is not at all sharply distinguished from certain groups of
Curculionidae (from Cossonides e.g.), but as the species have
somewhat different habits, and in the majority of cases can be
readily distinguished, it is an advantage to separate the two families.
About 1400 species are at present known. Most of them are wood-
and bark-feeders; some bore into hard wood; a few mine in twigs or
small branches of trees, but the majority live in the inner layers of the
bark; and this also serves as the nidus of the larvae. A small number
of species have been found to inhabit the stems of herbaceous
plants, or to live in dry fruits. Owing to their retiring habits they are
rarely seen except by those who seek them in their abodes, when
they may often be found in great profusion. The mother-beetle bores
into the suitable layer of the bark, forming a sort of tunnel and
depositing eggs therein. The young larvae start each one a tunnel of
its own, diverging from the parent tunnel; hence each batch of larvae
produces a system of tunnels, starting from the parents' burrow, and
in many species these burrows are characteristic in form and
direction, so that the work of particular Scolytids can be recognised
by the initiated.

The Platypides bore into the wood of trees and stumps; they are
chiefly exotic, and little is known about them. They are the most
aberrant of all Rhynchophora, the head being remarkably short, flat
in front, with the mouth placed on the under surface of the head,
there being no trace of a rostrum: the tarsi are elongate and slender,
the third joint not being at all lobed, while the true fourth joint is
visible. Hence they have not the appearance of Rhynchophora.
Some authorities treat the Platypides as a distinct family.

Some of the members of the group Tomicides also bore into the
wood. Recent observations have shown that there is an important
feature in the economy of certain of these wood-borers, inasmuch as
they live gregariously in the burrow, and feed on peculiar fungi that
develop there, and are called ambrosia. According to Hubbard[154],
some species cultivate these fungi, making elaborate preparations to
start their growth. The fungi, however, sometimes increase to such
an extent as to seal up the burrows, and kill the Insects by
suffocation.

Scolytidae sometimes multiply to an enormous extent, attacking and

destroying the trees in wooded regions. Much discussion has taken
place as to whether or not they are really injurious. It is contended by
one set of partisans that they attack only timber that is in an
unhealthy, dying, or dead condition. It may be admitted that this is
usually the case; yet when they occur in enormous numbers they
may attack timber that is in a sort of neutral state of health, and so
diminish its vigour, and finally cause its destruction. Hence it is of
great importance that they should be watched by competent
foresters.

The larvae of Scolytidae are said to completely resemble those of

Curculionidae: except in the group Platypides, where the body is
straight and almost cylindrical, and terminates in an oblique
truncation bearing a short hard spine.[155]

Fam. 83. Brenthidae.—Form elongate; rostrum straight, directly

continuing the long axis of the body, often so thick as to form an
elongate head; antennae not elbowed. The Brenthidae form a family
of about 800 species, remarkable for the excessive length and
slenderness of some of its forms, and for the extreme difference in
the sexes that frequently exists. It is well represented in the tropics
only, and very little is known as to the natural history and
development. These beetles are stated to be wood-feeders, and no
doubt this is correct in the case of the majority of the species; but Mr.
Lewis observed in Japan that Zemioses celtis and Cyphagogus
segnipes are predaceous, and enter the burrows of wood-boring
Insects to search for larvae as prey: they are very much modified in
structure to permit this; and as the other members of the group
Taphroderides are similar in structure, it is probable that they are all
predaceous. Nothing whatever is known as to the larval history of
these carnivorous forms. Indeed an uncertainty, almost complete,
prevails as to the early stages of this family. Riley has given a sketch
of a larva which he had no doubt was that of Eupsalis minuta, the
North American representative of the family; if he is correct the larva
differs from those of Curculionidae by its elongate form, and by the
possession of thoracic legs: these, though small, are three-jointed.
Descriptions, supposed to be those of Brenthid larvae, were formerly
published by Harris and Motschoulsky; but it is now clear that both
were mistaken.

Fig. 150—Eupsalis minuta. North America. A, Larva; B, pupa; C,

female imago; D, head of male. (After Riley.)

In the higher forms of Brenthidae the rostrum of the female is

perfectly cylindrical and polished, and the mandibles are minute,
hard, pointed processes placed at its tip. This organ is admirably
adapted to its purpose; it being used for boring a hole in wood or
bark, in which an egg is subsequently deposited. The males in these
cases are extremely different, so that considerable curiosity is felt as
to why this should be so. In some cases their head is thick, and there
may be no rostrum, while large powerful mandibles are present.

In other cases the rostrum is slender, but of enormous length, so that

it may surpass in this respect the rest of the body, although this itself
is so drawn out as to be quite exceptional in the Insect world:[156] the
antennae are inserted near the tip of the rostrum instead of near its
base, as they are in the female. The size of the males is in these
cases usually much larger than that of the female.[157] The males of
some species fight; they do not, however, wound their opponent, but
merely frighten him away. In Eupsalis it appears that the rostrum of
the female is apt to become fixed in the wood during her boring
operations; and the male then extricates her by pressing his heavy
prosternum against the tip of her abdomen; the stout forelegs of the
female serve as a fulcrum and her long body as a lever, so that the
effort of the male, exerted at one extremity of the body of the female,
produces the required result at the other end of her body. The New
Zealand Brenthid, Lasiorhynchus barbicornis, exhibits sexual
disparity in an extreme degree: the length of the male is usually
nearly twice that of the female, and his rostrum is enormous. It is at
present impossible to assign any reason for this; observations made
at the request of the writer by Mr. Helms some years ago, elicited the
information that the female is indefatigable in her boring efforts, and
that the huge male stands near by as a witness, apparently of the
most apathetic kind.

Coleoptera of uncertain position.

There are three small groups that it is impossible at present to place

in any of the great series of beetles.

Fam. 84. Aglycyderidae.—Tarsi three-jointed, the second joint

lobed; head not prolonged to form a beak. The two most important
features of Rhynchophora are absent in these Insects, while the
other structural characters are very imperfectly known, many parts of
the external skeleton being so completely fused that the details of
structure are difficult of appreciation. Westwood considered the tarsi
to be really four-jointed, but it is not at all clear that the minute knot
he considered the third joint is more than the articulation of the
elongate terminal joint. The family consists only of two or three
species of Aglycyderes, one of which occurs in the Canary Islands,
and one or two in New Zealand and New Caledonia. The former is
believed to live in the stems of Euphorbia canariensis; a New
Zealand species has been found in connection with the tree-ferna.
Cyathea dealbata

Fig. 151—Aglycyderes setifer. Canary Islands. A, Imago; B, tarsus

according to Westwood; C, according to nature; D, maxilla; E,
labium.

Fam. 85. Proterhinidae.—Tarsi three-jointed, the second joint lobed;

head of the male scarcely prolonged, but that of the female forming a
definite rostrum; maxillae and ligula entirely covered by the mentum.
As in the preceding family the sutures on the under side of the head
and prosternum cannot be detected. The minute palpi are entirely
enclosed in the buccal cavity. There is a very minute true third joint
of the tarsus, at the base of the terminal joint, concealed between
the lobes of the second joint. The family consists of the genus
Proterhinus; it is confined to the Hawaiian Islands, where these
Insects live on dead wood in the native forests. The genus is
numerous in species and individuals.
 Fig. 152—Proterhinus lecontei. Hawaiian Islands. A, Male; B, female;
C, front foot, more magnified.

Strepsiptera (or Rhipiptera, Stylopidae).—Male small or minute;

prothorax extremely small; mesothorax moderate, the elytra reduced
to small, free slips; metathorax and wings very large; nervuration of
the latter radiating, without cross nervules. Female a mere sac, with
one extremity smaller and forming a sort of neck or head.

Fig. 153.—Sexes of Strepsiptera. A, Male of Stylops dalii (after Curtis);

B, female of Xenos rossii (after von Siebold).

These curious Insects are parasitic in the interior of other Insects, of

the Orders Hymenoptera and Hemiptera. Their structure and their
life-histories entitle them to be ranked as the most abnormal of all
Insects, and entomologists are not agreed as to whether they are
aberrant Coleoptera or a distinct Order. The newly-hatched larva is a
minute triungulin (Fig. 154), somewhat like that of Meloe; it fixes
itself to the skin of the larva of a Hymenopterous Insect, penetrates
into the interior, and there undergoes its metamorphoses, the male
emerging to enjoy a brief period of an abnormally active, indeed
agitated, existence, while the female never moves. It is important to
note that these Strepsiptera do not, like most other internal
parasites, produce the death of their hosts; these complete their
metamorphosis, and the development of the parasite goes on
simultaneously with that of the host, so that the imago of the
Strepsipteron is found only in the imago of the host.[158] After the
young Stylops has entered its host it feeds for a week or so on the
fat-body (apparently by a process of suction), then moults and
assumes the condition of a footless maggot, in which state it remains
till growth is completed. At the latter part of this period the history
diverges according to sex; the female undergoes only a slight
metamorphic development of certain parts, accompanied apparently
by actual degradation of other parts; while the male goes on to
pupation, as is normal in Insects. (We may remark that the great
features of the development of the sexes are parallel with those of
Coccidae in Hemiptera.) When the Hymenopterous larva changes to
a pupa, the larva of the Strepsipteron pushes one extremity of its
body between two of the abdominal rings of its host, so that this
extremity becomes external, and in this position it completes its
metamorphosis, the male emerging very soon after the host has
become an active winged Insect, while the female undergoes no
further change of position, but becomes a sac, in the interior of which
young develop in enormous numbers, finally emerging from the
mother-sac in the form of the little triungulins we have already
mentioned. This is all that can be given at present as a general
account; many points of the natural history are still obscure, others
have been merely guessed; while some appear to differ greatly in
the different forms. A few brief remarks as to these points must
suffice.

Bees carrying, or that have carried, Strepsiptera, are said to be

stylopised (it being a species of the genus Stylops that chiefly infests
bees); the term is also used with a wider application, all Insects that
carry a Strepsipterous parasite being termed stylopised, though it
may be a Strepsipteron of a genus very different from Stylops that
attacks them. The development of one or more Strepsiptera in an
Insect usually causes some deformity in the abdomen of its host,
and effects considerable changes in the condition of its internal
organs, and also in some of the external characters. Great difference
of opinion prevails as to what these changes are; it is clear, however,
that they vary much according to the species, and also according to
the extent of the stylopisation. Usually only one Stylops is developed
in a bee; but two, three, and even four have been observed:[159] and
in the case of the wasp, Polistes, Hubbard has observed that a
single individual may bear eight or ten individuals of its Strepsipteron
(Xenos, n. sp.?).