CHEMISTRY

Leaving Cerificate Higher level

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CHEMISTRY
LEAVING CERTIFICATE HIGHER LEVEL

Jim McCarthy
Terence White
Cavan County Library
Withdrawn Stock

Edco |
The Educational Company of Ireland
 First published 2008

The Educational Company of Ireland

Ballymount Road
Walkinstown
Dublin 12
A member of the Smurfit Kappa Group

© Jim McCarthy and Terence White 2008

Editor: Antoinette Walker

Cover Design: Combined Media Company
Cover Image: iStockphoto
Design: Compuscript Limited
Photos: Science Photo Library

Printed in the Republic of Ireland by ColourBooks Ltd.

aper used in
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from Managed
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 Contents

Introduction Vil

Examination section vill

| Revised
a EseTmeTaTS ANC TG POMOGIC NC gay hepa rape lS opens i enh A BS 1 ce
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a OTN CR a RA ieed febPypd << 4 a 10
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ef
=f
pi! Pree eB ASCS 1am i nd fs =k ORS RRO Delete. eS 105 of
Tee ato ae,ws te scotoereeerenes
Ae SO, 112 a
(12 Oxidation Numbers and Redox littanonsz 5... 0 « Prva, MS 128 ely
4'3-Foels and Heats-of Reaction 42:c vs 4 ce devious iG omeeumangh. '. .140 tM
14 Fuels ana Heals of Reachuone ain ivulianid.
coduiee neta... 155 oA
‘ea1aR mTeS OMRCANION co ciao sk unis s SERS ee BIS eae erie ee, «OS, 169 O
C%6 Organic COMPOMIGS -:.> + Joes. Bink enerets Ot. Re Miia naeniags am: 184 mt
17 Biganiee nemical: Reactions fais o.oo. Matas) Be, CS es. 199 we
18 Chromatography and Instrumentation in Organic Chemistry ........... 218 M
Pe hence OUlingieitetkint 1s aactae: Wiest eclh FG resaelOeh
wm oe225 me
Be PCMAG. ya sac 0 in,oo en in MOUS SME LON TA we 238
ee. na -conien ts Bots toate Sh Dwonatl. «4, 290
MAE ANASS:hy. UD BADEN. DG FIMO, HUME... 256 O
l_23 YSU | UR Poet oer Jed re So oe ea A 2 268 O
PAGO Ieee
a GOT oer ari oniviuse. . 5.233

Questions from the 2008 Examination 301

Study Plan 303
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Experiments
‘a4 Flame tests (LinNa, KBacon amdt Cue: ae ter: eer eee ne 27

5 2(a)) Redox reactions of the:halogens..2..- 52 see eee 44

5.2(6) Displacement reactions Of metals. + 22 46

i224 ..1-lceoe

6.1 TeStS TOMENIONS. a... « ohn Se ee ee ee ee es 59

6.2 Recrystallisation of benzoic acid and determination
L of.its-meélting Dont RA eee 66
8.1 Determination of the relative molecular mass of a
volatile liquids. ties kbct aan eee Sere ORI. 92
ies Preparation of a standard (0.1 M) solution of
SOCIUMCarDONale ’it6.d aks wee i i ee fan ee 116
11.2 Standardisation of a hydrochloric acid solution
using a standard solution of sodium carbonate~........ 121
11.2(a) A hydrochloric acid/sodium hydroxide titration and the
use of this titration in making the salt sodium chloride... .122
11.3. Determination of the concentration of ethanoic
ACIG AO VINE OAL x... wien peeeaten eee, balce 124
11.4 Determination of the amount of water of crystallisation
in- hydrated sodium) carbonate 2) 2...
s+. ). cee 126
1221 A potassium manganate(VIl)—-ammonium iron(II)
Sulfate titration: .....2..:~ «deel eens eee. RS Pre 134
262 Determination of iron(II) in an iron tablet using a
standard solution of potassium manganate(VIl) ........ 135
12:3". Aniodine—thiosulitate: Craton. ccaeie «+gar sb cere cece eee 137.
12.4 Determination of the percentage (w/v) of
| hypechloritesin bleach Sayre.
20) ore eet Genera 139
1351 Preparation and properties of ethyne .............. waht
14.1. Determination of the heat of reaction of hydrochloric
acid: with-sodium AVGTONIGG es aus. cnac eens neers Oy ce 158
15.1. Monitoring the rate of production of oxygen from
hydrogen peroxide, using manganese dioxide
OSS CALAIS 5.5.4, 560.ike rscm les ter ae 169
15.2. Studying the effects on the reaction rate of
(i) concentration and (ii) temperature, using
sodium thiosulfate solution and hydrochloric acid
 ___ CONTENTS EGS
Experiments Revised
16.1 The extraction of clove oil from cloves by
L LO MPCIStUAUON ets. | thc coe ek ated, Caters as can eee 196) 6
PALE D Plepatationol SOapiee mea pacrssieit
tts <y Roc ene 20 «|=
17.2 Preparation and properties of ethene ................ 20j,ae 1)
17.3. Preparation and properties of ethanal ............... 210 3]
17.4 Preparation and properties of ethanoic acid ........... 212 O
18.1 Separation of a mixture of indicators using paper
ig SeMACIAMTEEENC
Ine©fa eee eee 2\9-ae le)
19:1 Simple experiments to illustrate Le Chatelier’s principle. . .233 |
22 Determination of free chlorine in swimming-pool water
or bleach using a colorimeter or comparator .......... 258 O
22.2(a) Determination of total suspended solids
(expressed as ppm) in a water sample by filtration ...... 260 fa
22.2(b) Determination of total dissolved solids
(expressed as ppm) in a water sample by evaporation .. .261 C
-22.2(c) Determination of the pH of a water sample ........... 262 [si]
22.3 Estimation of the total hardness of a water sample
PURGE ent i on) ae he Std Le ee oe 264. =? EE)
22.4 — Estimation of dissolved oxygen by redox titration ..... . .266 O
This logo indicates the main points you need to know

This logo indicates important information

This logo indicates an important experiment

 Introduction

tayout of chapters
The chemistry course is recognised as being a very long course. This book
is intended to provide a short, concise account of the entire course. The
information provided is based on:
@ the syllabus
@ questions from previous Leaving Certificate examinations.

The language used is straightforward and to the point. Diagrams and

photographs have been included where relevant. Key definitions are
highlighted and many ‘remember’ boxes are provided to help reinforce learning.

A covalent bond is formed when two atoms

share a pair of electrons. |
; Key definition

Remember...
The 3d sublevel is of higher energy | A point to remember
than the 4s sublevel.

In addition, key points are included at the end of every chapter.

The 28 mandatory practical activities are all included. They are located in
various chapters so that they are integrated with the theory of each activity.

The Study Plan on page 303 will help you to keep track of your revision.
® Work out how much time you have left before the exam and how much
time you can devote to each chapter.
Try to be realistic when setting your targets.
Tick off the boxes as you meet your goals.
Re-evaluate your plan if you feel you have been overambitious.
The night before’the exam, check that you have covered all key areas.
 Examination Section
How the course is divided
The chemistry course is composed of a core ga two options. The core is
covered in chapters 1 to 22, while options 1 and2 are dealt with in
chapters 23 and 24, respectively.

The examination paper

e Tinete are two.sections on the paper.
@ Each question carries 50 marks. Eight questions must be attempted.
@ There are three questions in Section A, all relating to mandatory
experiments.”
There are eight questions in Section B.
There are no compulsory questions.
At least two of the questions attempted must be from Section A.
Question 5 is likely to be based on material from the following chapters
in this book: -1, 2, 3,4, 5; Glande?
Question 6 is likely to be based on material from the following chapters
in this book: 13, 14, 16, 17 and 18.

Timing
@ Allow about 10 minutes for reading and selecting questions,
:
20 minutes for each question, and 10 minutes at the end for checking
over and, if necessary, finishing questions. a4

Topics covered in previous Higher Level exams

The table oni the next page shows a selection of the question Ba eis asked
about each of the mandatory experiments in recent years.
 EXAMINATION SECTION

64 10(adi) (a 4 (2004));,
ee 10(c) (2003
—-4(f) (2002)
= 3(2004)
hy

- 1

3
7(C)

22004)

10(0)
11(b), 9(b)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The following table shows a selection of the question numbers with parts
about each of the chapters in this book in recent years.

— Alb) af A(d) °
: 11(a) 10(a)

11(a) 5(a) 11(a)

Ala); 10(¢) 5(a)_ Ala); 5(a). 5(b); 10(b) 5; 10(b)_
10(bxi) 1 0(€)i)_ 11a) - A(i)
a -5(b) Bic) Sia) i

Sg oan aT
5(a)
16) 106) 3 EMR, 10(c)

Bow
fur
sa
©0 4(h); 10(a) 10(a)

oe
reais,

8(a)(b)
A(i) (2001
sample
paper)
106) 10) 10(b)

oo 9; 10(c)

Em ao :6
ee

9;11(a) 8 11(b) 7
re (ope
7 = 106) | Guan

OE 8(c)

sb) 7d) NO)

ie
ue 2 ie | i
11(c) | (0 noe | 110
 _EXAMINATION SECTION
Eraw nine
@ When you receive your exam paper, spend a few minutes examining the
content of the various questions. Decide fairly quickly which ones you
can do best. Answer those questions first, but do not exceed the
recommended 20 minutes per question limit.
@ Do not waste too much time trying to think of answers to particular
parts of a question. Leave spaces and come back to these later.
@ If you are attempting question 4, it is a good idea to attempt all
11 parts. You will be marked on the best eight.
@ Remember to attempt all parts of all the other questions that you
choose (except for questions 10 and 11, and questions on the Options).
@ It is very important to show the starting point and the various stages in
every calculation, so that the examiner can follow what you are doing.
@ Ifa labelled diagram is specified in the question, this must be included
in your answer.

Common mistakes
@ Not rie he. paper ponecty.
@ Not finishing the paper.
@® Ignoring the marking scheme — you must take the marking scheme
into account when you allocate time to each question or part of a
question.
@ Missing part of a question: when checking your work at the end of the
exam, make sure that you have done all of the parts specified in each
question.

Past Questions and Answers

The following question and answer is based on a past Leaving Certificate paper
and marking scheme. These are provided on the State Examinations
Commission website at www.examinations.ie

Sample question
(a) The hydrocarbon molecules iin petrol typically contain carbon chains
with between five and 10 carbon atoms. The most widely used
petrol in Ireland has an octane number of 95.
(i) |What is meant by the octane number of a fuel?
(ii) |The two hydrocarbons used as references when establishing
the octane number of a fuel are heptane and 2,2,4-
trimethylpentane. Draw the structure of each of these
molecules. *
(continued)
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Crude oil is separated into a number of fractions in oil

(ili)
refining. Name the two fractions which contain molecules
with the carbon chain lengths needed for petrol. (6)
(iv) Dehydrocyclisation is one of the processes used to increase
the octane numbers of hydrocarbons. What two changes
to the hydrocarbon molecules occur during this process? (6)
(v) Ethanol is an example of an oxygenate. Give another
example of an oxygenate. Give two reasons why
oxygenates are added to petrol. : (9)
(b) Write a balanced chemical equation for the combustion of
ethanol, C,H.OH. Given that the heats of formation of ethanol,
carbon dioxide and water are —278, —394 and —286 kJ mol",
respectively, calculate the heat of combustion of ethanol.

Sample answer
(a) (i) Measure of tendency (likelinood) to auto-ignite (5)
(ii) Heptane: CH,CH,CH,CH,CH,CH,CH, - (3)
2,2,4-trimethylpentane: (CH3);CCH,CH(CHS), (3)
(iii) .Light gasoline (3)
Naphtha (3)
(iv) Removal (loss) of hydrogen (3)
Ring formation (3)
(v) Methyl-t-butyl ether (3)
Raise octane number (3)
Less harmful to the environment (3)

(b) C,H,OH + 30, - 2CO, + 3H,O —(ep)—

(An = YAH, (products) — 2AH,(reactants)

AH = 2 x —394 / —788 (3) + 3 x -286 / -858 (3) — {+278 (3) + 0}
OR
2 x —394 / —788 (3) + 3 x-286 / -858 (3) + 278 (3) — 0

AH = -1368 (3)

(xii)
 CHAPTER 1
Elements and the Periodic Table

@ © Topics Covered in this Chapter

@® Elements and their symbols
History of the idea of elements
The periodic table of the elements
History of the periodic table
Properties of elements within the main groups

Elements and their symbols

Pure substances are either compounds or elements. Compounds can be
chemically broken down into the elements of which they are made.

Elements cannot be broken down chemically into simpler substances.

There are more than 110 different elements known.

An element is a substance that cannot be broken down into simpler

substances by chemical means.

Each element is designated by a symbol and has its own unique atomic
number. You are required to know the symbols of all elements with atomic
numbers from 1 to 36.

History of-the idea of elements

The idea of elements was first thought of by the
ancient Greeks, notably Empedocles. In about Bc 450,
Empedocles defined elements as the basic substances
from which all other materials are made. He stated
that there were four elements: earth, air, fire and water.
Kot
Sor GU) uy,

)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Robert Boyle Humphry Davy Henry Moseley

More than two thousand years later, Robert Boyle defined an element as a
substance that cannot be broken down into simpler materials. If a
substance could be broken down into simpler materials, then it definitely
was not an element.

The next advances were due to Humphry Davy, who developed powerful
new electrochemical techniques for breaking down compounds into
elements: He isolated the elements potassium, sodium, barium, strontium,
calcium and magnesium.

The next major step in the development of the concept of element

was due to the English physicist Henry Moseley. In London in 1913,
using X-rays, he found that the atomic nucleus of each element had
a charagteristic positive charge. He called this charge the atomic
number: .f*

petty
AAn elamy it is a substance whose atoms all have the same
«Ss ¥ 7 ~

if.
fe atomic number. ;
Po

The periodic rable of the elements

In the periodic table of the elements, elements with similar chemical
properties are grouped together.

In the periodic table, elements are arranged in order of increasing atomic

number. Elements that have similar chemical properties are placed in vertical
columns called groups. For example, chlorine is in Group VII and has
chemical properties that are similar to the other Group VII elements, e.g.
fluorine, bromine and iodine.
 ELEMENTS AND THE PERIODIC TABLE

IIA
IA
A Al

31qe} 21powed ays LL “614

fi.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The elements between Groups II and IJI are known as the d-block
elements. Each vertical group in this region of the table is known as a
subgroup: for example, copper, silver and gold make up the copper
subgroup.

Directly above the symbol of each element in the periodic table is written
its atomic number. The relative atomic mass is written underneath the
symbol. For example, chlorine (Cl) can be seen to have an atomic number
of 17 and a relative atomic mass of 35.453.

17,
Cl
35.453

A horizontal row of elements in the periodic table is called a period. The

first period contains two elements, hydrogen and helium. There are eight
elements in the second period, starting with lithium and ending with neon.
There are also eight elements in the third period, starting with sodium and
ending with argon. There are 18 elements in the fourth period, starting
with potassium and ending with krypton.

History of the periodic table

baw ofTriads
In 1817, Johann Dobereiner, a German
chemist, recognised that three recently
discovered elements, calcium, strontium and
barium, had properties that were quite similar.
He also noticed that the atomic weight of
strontium was almost midway between that of
calcium and barium. He called this group of three
elements a triad. Dobereiner thought that the
elements fitted together in threes. His discovery
became known as the Law of Triads. However,
only a small number of triads was found to
Johann Dobereiner
exist. Two other triads of elements found by
Dobereiner were chlorine, bromine and iodine,
and lithium, sodium and potassium, respectively.
 _ELEMEAND
NTS THE PERIODIC TABLE [0

law of Octaves
In 1863, the English chemist John Newlands
arranged the elements in order of atomic weight and
found that properties seemed to repeat themselves
every eighth element. However, this periodic
relationship worked for only the first 17 elements
then known. Newlands attempted to force all the
known elements to fit the pattern but was
unsuccessful. Newlands’ Law of Octaves was not
accepted by other chemists.

John Newlands

Mendeleev’s periodic table

Some years later, Dmitri Mendeleev, a Russian
chemist, found that there was a periodic recurrence
of properties when the elements were arranged in
order of their atomic weights. He placed elements
that were similar to each other in groups.
Mendeleev, however, in his periodic table published
in 1869, listed separately in subgroups elements
such as copper and silver whose properties did not fit
in with those of the main groups. In Mendeleev’s
table, the first two horizontal periods contained
seven elements, but the next two contained 17 each.
Dmitri Mendeleev

Mendeleev put the elements iodine and tellurium out of the correct order
of their atomic weights because of their properties. He put tellurium in
what we now know as Group VI, and iodine in what we now know as Group
VII, even though iodine has the smaller atomic weight. He also left gaps in
the table in order to make elements fit into proper groups, and predicted
the properties that the missing elements ought to have. The subsequent
discovery of the elements gallium, scandium and germanium showed the
accuracy of the*predictions.

Fig. 1.2 Some of the gaps left for undiscovered elements in Mendeleev's table

)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

One of the apparent anomalies in Mendeleev’s table — the placing of

tellurium (atomic weight 127.6) before iodine (atomic weight 126.9) — was
finally explained after Moseley discovered in 1913 that each element had a
different atomic number. In the modern periodic table, elements are
arranged in order of atomic number, not atomic weight. Tellurium (atomic
number 52) comes before iodine (atomic number 53).

(a) Mendeleev’s periodic table (elements mainly in order of atomic weight)

(b) Modern periodic table (elements in order of atomic number)

Fig. 1.3 lodine and tellurium in the periodic table

Remember...
If the first 36 elements were arranged in order of relative atomic mass,
the arrangement would differ from their order in terms of atomic number
as follows: potassium would come before argon, and nickel would come
before cobalt. °

Differences between Mendeleev’s periodic table and the modern

periodic table
Table 1.1

Modern periodic table ©

Gaps left for undiscovered elements Gaps have been filled
Group
0 elements missing Group 0 elements included
Elements discovered since 1869 Rlements discovered since 1869
missing — included

d-block elements arranged as d-block elements arranged as

subgroups beside each main group subgroups in a separate block

Elements arranged in order of Elements arranged in order of

increasing atomic weight (in almost increasing atomic number
all cases)
 __ ELEMENTS ANDTHE PERIODIC TABLE

prapaetics ofneueats withinthetmain groups

Within a group, there are similarities in the physical and chemical
properties of the elements. The most reactive elements are the Group I and
Group VII elements.

The alkali metals

The Group I elements are called the ANAR metals. They are all eee
reactive metals, increé asing in reactivity down the group.
@)
Some properties that these elements have in common are as follows:

Physical properties
@ They are soft metals.
@ They have low densities.

Chemical properties
@ When they are freshly cut, they have a metallic shine, but this
disappears rapidly due to the reaction of the exposed metal surface
with oxygen in the air. The metal oxide is formed.
@ They also burn readily in air, forming the metal oxide.
@ Sodium reacts as follows:
4Na + 0, > 2Na,O
@ They react vigorously with water, forming a basic solution
0! and
hydrogen. For example, sodium reacts as follows:
2Na + 2H,O — 2NaOH + H,
Alkali metals are stored in oil to prevent reactions with water and with
atmospheric oxygen.

The alkaline earth elements

SOHOSRTCHE PHOTO ASHESHSEHHOAHEHHEESHRHESHHOOHH
OTHE OHHHEREREOEHTTHEOSETHESSHESEHRHSHEHHTHEHHHHHHTHABTHOE

The Group II elements are called the alkaline earth elements. Tey" are
all reactive elements, with reactivity increasing down the group.
b

Some properties that magnesium and calcium have in common are as follows:

Physical properties
@ They are metals which are harder than the alkali eels

Chemical properties
@ They are less reactive than the corresponding alkali metals. For
example, calcium reacts less vigorously with water than the
corresponding alkalt metal potassium.
Calcium + water — calcium hydroxide-+ hydrogen Gi
ee LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The halogens iy ES
The Group VII elementsi are alle the balocens aiken are very reactive
non-metals, decreasing.in reactivity down the group.
ae Wy
a»

Some properties that these elements have in common are as follows:

Physical properties
@ They have low_melting and boiling points.
@ At room temperature, fluorine and chlorine are yellow-green gases,
bromine is a red liquid and iodine is a dark solid.

Chemical properties
@® They react with hydrogen to form compounds which dissolve in water
to form acidic solutions. For example, in the case of chlorine:
Hq) + Clog) ~ 2HCI)

Hydrogen chloride gas dissolves in water to form hydrochloric acid

solution.
@ They react vigorously with sodium (and the ae alkali metals),
forming white salts. For example:
Sodium + chlorine — sodium chloride

The noble gases

‘The ees 0 elemene arepeed the noble gases. Tic main properties that
these elements have in common are as follows:

Physical properties
@ They are all gases at room temperature.
@ The boiling point and density increases going down the group.

Chemical properties
@ They are the least reactive of all elements.

s-block and p-block elements

The elements in Groups I and I ona astocks aiereactiveen erate eaiiea: che
s-block elements. They have lower densities, lower melting points and
lower boiling points than most other metals. They are also more reactive
than the d-block metals.

The elements in Groups III, IV, V, VI, VII and 0 are called the p-block
elements. These are mainly non-metals, but the lower members of some of
these groups, for example tin and lead in Group IV, are metals.
 ELEMENTS AND THE PERIODIC TABLE
Specified Demonstration: The reaction of alkali metals
with water
The chemical equations for the reactions between alkali metals and water in
this demonstration are as follows:
| 2Li. + 2H,O,) > 2LIOH;,.) + H 2(g)
/* 2Na,,) + 2H,O,) > 2NaOH,,9) + Haig)
2K/. + 2HOy > 2KOH,,4 + H 2(9)

Procedure
1 Place a small piece of lithium in a trough of water. The lithium slowly
moves across the surface of the water as it reacts.
2 Place a small piece of sodium in a trough of water. The sodium rapidly
moves across the surface of the water as it reacts.
3 Place a small piece of potassium in a trough of water. The potassium
moves very rapidly across the surface of the water as it reacts, catches fire
with a lilac flame, and explodes.
4 Ifa piece of red litmus paper is dipped into the trough after any of the
alkali metals have been added to water, it turns blue. This indicates that
an alkaline solution has been formed (lithium hydroxide, sodium
hydroxide and potassium hydroxide are all bases).

This demonstration shows clearly that potassium is the most reactive of the
three metals, followed by sodium, while lithium is the least reactive of the three.

An element is a substance that cannot be broken down into simpler

substances by chemical means.
In Mendeleev’s periodic table (1) gaps were left for undiscovered elements,
(2) the Group O elements weré missing, (3) elements discovered since
1869 were missing, (4) d-block elements were arranged as subgroups
beside each main group, and (5) elements were arranged in order of
increasing atomic weight (in most cases).
In the modern periodic table (1) gaps were filled, (2) Group O elements
were included, (3) elements discovered since 1869 were included,
(4) d-block elements were arranged as subgroups in a separate block,
and (5) elements were arranged in order of increasing atomic number.
 CHAPTER 2
Atomic Structure

@@ © Topics Covered in this Chapter

John Dalton’s atomic theory
Thomson and the electron
The nucleus
Protons and neutrons be
Properties of electrons, protons and neutrons
Atomic number (Z)
Mass number (A)
Isotopes
Relative atomic mass (A,)

Ideas about atoms

It is generally accepted that matter is composed of minute particles, which
may be atoms, molecules or ions.

John Dalton’s atomic theory

In the early 1800s, John Dalton was able to provide
indirect evidence for the existence of atoms. Dalton’s
ideas included the following:
@ Atoms are indivisible and indestructible.
@ The atoms of a given element are identical to
each other, and have the same mass and
chemical properties.
@ Atoms of different elements vary in mass.
@ A compound contains atoms of two or more
elements combined together in fixed
proportions. John Dalton

Using his theory, Dalton was able to account for experimentally based laws
of chemistry, such as the law of conservation of mass.
 ATOMIC STRUCTURE

The law of conservation of mass states that matter is neither

created nor destroyed in the course of a chemical reaction.

Thomson and the electron

A discharge tube is a long glass tube fitted with a metal electrode at each
end. When the gas inside is at a very low pressure, passing electricity
through the tube results in invisible rays travelling in straight lines from
the cathode — the negative electrode — to the anode — the positive electrode.

William Crookes showed that these rays, which

were called cathode rays, travelled in straight lines,
and that small objects placed in the path of the rays
cast a sharp.shadow in the fluorescence at the endof
the tube. This convinced him that cathode rays
consisted of particles.

William Crookes

In 1897, JJ Thomson, at the Cavendish Laboratory

in Cambridge, showed that cathode rays were
attracted by the positive plate in an electric field.
This meant that they had a negative charge.
Thomson measured the ratio of charge to mass
(e/m) for the particles. He found that these
negatively charged particles were about 2000 times
lighter than hydrogen atoms and were to be found
in all matter. A eee

The Irish scientist George Johnstone Stoney

anticipated the existence of negative particles. His
suggested name for them, electrons, was then
adopted for the particles found by Thomson.

George Johnstone

wy)
Stoney
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

In 1911, the American scientist Robert Millikan

devised and conducted his famous oil drop
experiment which allowed the charge on the
electron to be measured accurately.

Robert Millikan

Thomson’s plum pudding model

Thomson suggested that atoms were positively charged spheres in which
negatively charged electrons were embedded, similar to a plum pudding.
However, this model was soon shown to be inadequate.

©= electron

_ Fig. 2.1 Thomson's plum pudding model of the atom

The nucleus
Ernest Rutherford directed his assistants Geiger
and Marsden to fire alpha particles at very thin gold
foil. They used a zinc sulfide screen to detect
scattered alpha particles. Most of the alpha particles
were not deflected at all, showing that they had
passed through basically empty space. Some
particles were deflected at small angles. A small
number of particles were deflected at angles greater
than 90°, and a very small number actually
bounced back towards their source.
Ernest Rutherford
 _ ATOMIC STRUCTURE
Rutherford explained that the deflection of the alpha particles was due to
their going close to and being repelled strongly by a dense concentration of
positive charge. The alpha particles that bounced back did so because they
collided with a small dense mass.

He proposed that nearly all of the mass of the atom is densely concentrated
in a tiny positively charged central region called the nucleus, and the rest
of the atom is mostly empty space. The electrons move around in the rest of
the atom’s volume, balancing the positive charge ofthe nucleus and keeping
the atom neutral.

Protons and neutrons

Rutherford found that protons made up the positive part of all atoms.

Rutherford could explain the charge on the nucleus

(but not all of its mass) in terms of the number of
its protons. He suggested that the nucleus also
contained other particles of equal mass to protons,
but with no charge. In 1932, James Chadwick
produced the evidence for these particles, which
were called neutrons.

James Chadwick

Properties of electrons, protons and neutrons

The masses, charges and locations of electrons, protons and neutrons are
summarised in Table 2.1.

Table 2.1

Electron . 1836 <4

Proton 1 +1 In the nucleus

Neutron 1 0) In the nucleus

LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Atomic number (Z)

All atoms of the same element contain the same number of protons. This
number of protons identifies what element it is. The English physicist
Henry Moseley called the number of protons in the nucleus the atomic
number. It is given the symbol Z.

The atomic number of an element is the number of protons in

the nucleus of an atom of the element.

The atomic number gives three pieces of information about an element:

1 The number of protons in the nucleus of an atom of the element.
2 The number of electrons in an atom of the element.
3 The position of the element in the modern periodic table.

Mass number (A)

The mass number of an atom is the sum of the numbers of protons and
neutrons in the nucleus of the atom. It is given the.symbol A. The number
of neutrons can be calculated by subtracting Z from A, i.e. number of
neutrons = A — Z.

The mass number of an atom is the sum of the numbers of

protons and neutrons in the nucleus of the atom.

Information about an atom can now be written more fully by including the
atomic number and the mass number. For example:
19
FE
9

The subscript 9 is the atomic number, Z, and the superscript 19 is the mass
number, A. The number of neutrons = A —- Z = 19=~9= 10.

Example 2.1

State the number of protons and neutrons for the calcium atom, ac
SZ ——

Answer
The atomic number Z = 20, so there are 20 protons. The mass number A = 40.
Number of neutrons = A — Z = 40 — 20 = 20.
 ___ATOMIC STRUCTURE
Example 2.2
An atom of argon has 18 protons and 22 neutrons. Indicate the mass number
and atomic number for the atom.

Answer
Since the number of protons is 18, the atomic number Z = 18.
The mass number A = the sum of the numbers of protons and neutrons
=18.4 22 = 40

Isotopes
Atoms with the same number of protons but different numbers of neutrons
are called isotopes. In other words, isotopes have the same atomic number
(Z) but different mass numbers (A).

Isotopes are atoms with the same number of protons but different
numbers of neutrons.

Naturally occurring hydrogen consists of three isotopes: 'H (1 proton

and no neutron); 7H (1 proton and 1 neutron); and *H (1 proton and
2 neutrons). The 'H isotope is by far the most abundant isotope of
hydrogen.

—o— -o— se POE

oS 4
(NS \ 6 ({ 6p . °
6 | ae
LOhe ree
NE )
/
a ee Nasesroc
Age He &
Fig. 2.2 The isotopes of carbon

Naturally occurring carbon consists of three isotopes: carbon-12 (i.e. '’C,

with 6 protons and 6 neutrons); carbon-13 (i.e. '°C, with 6 protons and
7 neutrons); and carbon-14 (i.e. 14C with 6 protons and 8 neutrons).

©
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Relative atomic mass (A,)

The relative atomic mass of an element is the average -
mass of an atom of the element relative to 1/12th the _
mass of an atom of carbon-12.

7 Example 2.3
In a sample of silicon, 92.2% of the atoms are silicon-28, 4.7% are silicon-29 ©
and 3.1% are silicon-30. Calculate the relative atomic mass, A, of silicon. _

_ Answer
The abundance of each isotope is motile byits mass, the sum of these
products is calculated and the result divided by 100.
A,(Si) = (92.2 x 28)+(4.7 x 29)+(3.1 x 30)]/ 100
_ = (2581.6 + 136.3 +93]/100 |
: = 2810.9/ 100
S84 a

The atomic number of an element is the number of protons in the

nucleus of an atom of the element.
The mass number of an atom is the sum of the numbers of protons and
neutrons in the nucleus of the atom.
Isotopes are atoms with the same number of protons but different numbers
‘of neutrons. ‘
The relative atomic mass (A,) of an element is the average mass of an atom
of the element relative to 1/12th the mass of an atom of carbon-12.

Your revision notes

 CHAPTER 3
Radioactivity

@@ © Topics Covered in this Chapter

The discovery of radioactivity

What is meant by radioactivity?
Types of radiation
Distinction between nuclear and chemical reactions
Radioisotopes and half-life
Background radiation
Uses of radioisotopes

The discovery of radioactivity

Henri Becquerel wrapped a photographic plate in
black paper, put crystals of auranium compound on
it, and placed it in a dark place. A few days later, he
developed the plate and found an image of the
crystals. He concluded that the crystals themselves
had emitted the radiation that had caused the
image on the photographic plate.

The Polish chemist Marie Curie

and her husband Pierre carried out
further research on uranium
compounds and other substances
that emitted ~ this radiation
discovered by Becquerel. Marie
Curie called this newly discovered
radiation radioactivity. The Curies
isolated two new elements from the Marie and Pierre Curie

radioactive pitchblende ore within a

few years. These elements — polonium and radium — are much more
radioactive than uranium.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

What is meant by radioactivity?

Radioactivity is defined as the spontaneous breaking up of

certain unstable nuclei, accompanied by the emission of radiation.

Types of radiation
There are three types of radiation emitted by radioactive isotopes:
@ « particles, which have a positive charge.
@ § particles, which have a negative charge.
@ y rays, which are neutral.

a particles (alpha particles)

These particles consist of two prorere nadetwo neutrons, i.e.
eh are (helen
nuclei. They move relatively slowly and are stopped quite easily, for
example.by human skin or by a few sheets of paper.

Alpha particles are helium nuclei, with a positive charge

and little penetrating ability.

An example of an @ emitter is americium-241, which is used in many

smoke detectors. It decays according to the following equation:
241 237 4
Am— Np+ He + energy
95 93 2
The new element formed is neptunium.

B particles (beta particles)

SHHOHSHOSSHHROTSHHHHOOHAHSHHSHHTHOHSSSOSTSSHHOHSHHSHHSSSHSTHHOHTHKSHESHOTERSESHESHROBSAHEEESSEHESHEESSS

In some radioactive elements, neutrons disintegrate into pratone and

electrons. The electrons — B particles — are emitted from the atom in a fast-
moving stream. They are more penetrative than @ particles but can be
stopped by a 2—3 mm thickness of aluminium.

Beta particles are electrons, with a negative charge and

greater penetrating ability than alpha particles.
Peas eae Fhe _______ RADIOACTIVITY. @
Carbon-14, which is used to determine the age of things, is an example of a
B emitter. It decays according to the following equation:
14 14 0
C+ N+ e+ energy
6 7 =i

The atomic number increases by one, which means that a new element,
nitrogen, is formed.

y rays (gamma rays)

SCOTHSH
CEH TEREHH ESOS
O OSES eeeosenrseeceseces

The third type of radioactivity sews By reclcacrive ela isalore of

energy called y rays. These rays have no mass or charge. They move very
quickly and have much greater penetration than @ or B radiation. Thick
shields of concrete or lead can stop them.

Gamma rays are high-energy electromagnetic radiation,

with greater penetrating ability than beta particles.

An example of a y emitter is cobalt-60, which is used for cancer treatment

and for food irradiation.
60 60
Go = or Ini
27 27

The equation shows that no new element is formed, but energy is emitted.

Distinction between nuclear and chemical reactions

Table 3.1 Differences between nuclear and chemical reactions

Nuclear reactions reactic

New element may be formed New element not formed —
Changes occur in nucleus No change in nucleus
No chemical bonds broken or formed Chemical bond-breaking and
forming occurs

be

When an isotope undergoes beta decay, its atomic number increases by 1,

while its mass number remains unchanged.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 3.1 o
Write an equation for the beta decay of the radioactive isotope P
15

Answer
When the 22P isotope undergoes beta decay, its atomic number increases
by 1, while its mass number remains unchanged.
32 32 0
P55 S- e

When an isotope undergoes alpha decay, its atomic number decreases by 2,

while its mass number decreases by 4.

Example 3.2 222

Write an equation for the alpha decay of the radioactive isotope Rn
86
Answer
When the 222Rn isotope undergoes alpha decay, its atomic number decreases
by 2, while its mass number decreases by 4.
222 218 4
Rn— Po + He
36 34 z

Radioisotopes and half-life

Unstable, radioactive isotopes are called radioisotopes. Carbon-12, for
example, is stable, whereas carbon-14 is a radioisotope.

Radioactive atoms decay in such a way that the number of them present is
halved after a fixed interval of time passes. This interval of time is called the
half-life of the sample. Some radioisotopes decay very quickly and have
short half-lives.

The half-life of a radioactive isotope is the time taken

for half of the atoms in a sample of the isotope to decay.

Background radiation
A low level of ionising radiation surrounds us at all times.
@ More than half of the background radiation is caused by radon gas. This
is formed by the decay of radioisotopes found in rocks in the ground.
Radon barriers are incorporated into new buildings to prevent the gas
seeping into the buildings.
 ___ RADIOACTIVITY
@ The artificial sources of background radiation are mostly medical. They
include cobalt-60, which is used in cancer treatment, and medical X-rays.

Uses of radioisotopes
Radioisotopes have many uses and are particularly important in
archaeology, in medicine and in food preservation.
@ Archaeology: Carbon dating is an important method used for
estimating the age of objects that contain carbon, such as paintings,
fabrics and wood. Carbon-14 is a radioisotope emitting B particles
and it has a half-life of over 5000 years. When an animal or plant is
alive, it will have carbon-12 and carbon-14 in the same ratio as is
present in the air. After the death of the organism, the unstable carbon-
14 decays, while the stable carbon-12 remains unchanged. By
measuring the changed ratio, and using the value of the half-life of
carbon-14, the age of the object can be estimated.
@ Medicine: Cobalt-60, ay ray emitter, is used in the treatment of cancer
with radiation, i.e. radiotherapy.
@ Food preservation: Food preservation is carried out by irradiating the
food using Y rays emitted by cobalt-60.

Specified Demonstration: Properties of a, B

and y radiation
Chemicals needed
a a, B abd y sources.
@ Range of absorbers: sheets of paper, 3 mm sheet of aluminium, 4 cm
block of lead.

Procedure
eeeoereeeeseaere

1 Assemble Ae Raion as uf in the ie Gat ho any

radioactive source present).
2 Measure the average background count per minute.
3 Place an & source 4cm from the Geiger-Miiller tube window and take
a count for dne minute. Subtract the average background count and
record your results.
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Counter

Absorber
Radioactive
source

Geiger-Muller tube

Fig. 3.1 Geiger-Miller tube

4 Repeat for the B and y sources. Subtract the average background count
from each reading and record your results.
5 For each of the sources, place the paper, aluminium and lead in turn
between the source and the Geiger-Miiller tube window. Subtract
the average background count from each reading, and record your
Fesultsa0 |

Remember...
| The paperis sufficient to block the alpha radiation, while the
aluminium blocks the beta radiation, and the thick block of lead is needed
to block the gamma radiation.

Alpha particles

Beta particles
© S)

Gamma rays He

Sheet of paper 5mm aluminium Thick lead

Fig. 3.2 The relative penetrating powers of alpha, beta and gamma radiation

This demonstration shows clearly that gamma radiation is the most

penetrating of the three types of radiation, followed by beta particles, while
alpha particles are the least penetrating of the three.

2
 _ RADIOACTIVITY —

Radioactivity is defined as the spontaneous breaking up of certain

unstable nuclei, accompanied by the emission of radiation.
Alpha particles are helium nuclei, with a positive charge and little
penetrating ability.
Beta particles are electrons, with a negative rane and greater
penetrating ability than alpha particles.
Gamma rays are high-energy electromagnetic radiation, with eae
penetrating ability than beta particles. =
__In a nuclear reaction (1) a new element may be formed, (2) changes occur
"in the nucleus, and (3
(3) no chemical bonds are broken or formed.
In a chemical reaction (1) a new element is not formed, (2) there is no
change in the nucleus, and (3) chemical bond-breaking and forming occurs.
The half-life of a radioactive isotope is the time taken for haltof the atoms
~ ina sample of the isotope to decay.

What are isotopes?

Define relative atomic mass, Ar.
What is the principle on which the mass spectrometer is based?
Calculate the relative atomic mass of a sample of lithium, given _
that a mass spectrometer shows that it consists of 7.4% of °Li
and 92.6% of Li.

Your revision notes

 CHAPTER 4
Electronic Structure of Atoms

@@© Topics Covered in this Chapter

Bohr’s model of the atom
Energy levels in atoms
Emission and absorption of light by elements
Spectral series
Absorption spectra
Line spectra as evidence for energy levels
Atomic orbitals
Electronic configurations of atoms and ions
Atomic radii
Ionisation energies
The periodic table and electronic structure

Bohr’s model of the atom

In 1913, Danish physicist Niels Bohr put forward a
theory of the hydrogen atom. He stated that:
@ The hydrogen electron is “restricted to those
regions of the atom that have certain energy
values (energy levels).
@® When an electron moves from a higher level
of energy (E,) to a lower level of energy (E,):
a definite amount of energy equal to the
energy difference between the two levels is
emitted:
Bo LL hf, where h = Planck’s constant and Niels Bohr
f = frequency of the light emitted.
@ If an atom absorbs an amount of energy equal to the energy difference
between the energy level (E,) the electron is in and a higher energy level
(E,), the electron will move to the higher level. Again, ESS he
@ Associated with each energy level is an integer, n, called the principal
quantum number.
 ELECTRONIC STRUCTURE OF ATOMS =f

Fig. 4.1 Energy levels in atoms

Bohr’s model worked well for hydrogen, but less well for other atoms.

Energy levels in atoms

Ce energy level is a region of definite energy within the atom

-—. that electrons
can occupy.
ti x
i!

/
Electrons in atoms occupy energy levels that are outside the nucleus.
Different energy levels in atoms have different energy values, and have
different capacities for electrons.

Table 4.1 Energy levels and electron capacities

i LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Table 4.2 Electrons in first 20 elements in periodic table

‘Element Atomic number _Electror

=} I — = N =) I] WwW

Hydrogen 1 1
Helium 2 z
Lithium S yh 1
Beryllium 4 2 2
Boron 5 2 3)
Carbon 6 5 2 4
Nitrogen 7 2 5
Oxygen 8 2 6
Fluorine 3 2 7
Neon 10 a 8
Sodium 11 2 8 1
Magnesium 12 2 8 2
Aluminium 13 2 8 a
Silicon 14 2 8 4
Phosphorus 15 2 8 5
Sulfur 16 2 8 6
Chlorine ~ 17 2 8 Z
Argon... 18 a2 8 8
Potassium 19 2 8 8 1
Calcium 20 2 8 8 2-

(ose
Po eee = i _~o~

‘~@\ ()
\ pre fot \ 9 |
Se Prisfe hari © equ}
\ A | ete hana
“One” IP, See ee We ee
Fluorine (2,7) isa eomente we
on r*
i eel

Chlorine (2, 8, 7)

Fig. 4.2 Arrangement of electrons in atoms of the Group VII elements

 ELECTRONIC STRUCTURE OF ATOMS
In general, elements in the same group of the periodic table have the same
number of electrons in the outermost energy level of their atoms. The only
exception to this is helium in Group 0. It has just two electrons in the outermost
energy level of its atoms, unlike neon and argon which each have eight.

Emission and absorption of light by elements

Many elements and their salts, when vaporised in a flame, emit light. The
light emitted has a colour characteristic of the particular element.

Mandatory Experiment 4.1: Flame tests (li, Na,

K, 6a, Sr and Cu)
Procedure
1 In the fume cupboard, clean
the platinum wire using con- Colour seen here
centrated hydrochloric acid.
2 Crush the salt to be tested ~ Platinuin wire
with a pestle and mortar. I
3 Dip the platinum wire in
concentrated hydrochloric
acid and then in the salt to Fig. 4.3
be tested.
4 Place the platinum wire in the flame of the Bunsen burner (Fig. 4.3)
and note the colour given off.
5 Repeat the experiment for each of the other salts. Again, note the
colour in each case.
6 The expected results are shown in Table 4.3.

Table 4.3

Element. _ Flame colour

Barium UES, Yellow-green
Copper i Blue-green
Lithium Deep red
Potassium Lilac
Sodium Yellow
Strontium Red
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The colours that particular elements, such as strontium and barium, emit
in a flame are often seen in firework displays. For example, strontium
nitrate is used to give a red colour in fireworks, while barium nitrate gives
a green colour.

If an element is a gas, like neon, or is easily vaporised, like mercury or

sodium, it will emit light of a characteristic colour when placed in a
discharge tube at low pressure and subjected to a high voltage.

Cathode (- Anode (+
gucci ane Evacuated glass tube honed,
containing a gas at
low pressure

Fig. 4.4 Discharge tube

For example, a sodium discharge tube emits yellow light when subjected to
a high voltage. Yellow streetlights are a type of discharge tube containing
sodium vapour.

A spectroscope can be used to analyse the light emitted by elements. When

the light emitted from a discharge tube containing hydrogen is analysed
using a spectroscope,.a series of coloured lines of definite wavelength
against a dark background is observed. This type of spectrum is called a line
spectrum. a

The emission spectra of other elements are also line spectra. The emission
spectrum of an element is characteristic of that element, and is different
from that of any other element.

A line spectrum is a series of coloured lines against a dark

background.
 __ ELECTRONIC STRUCTUREOFATOMS |
Specified Demonstration: Observation of line
spectra of elements using a spectroscope
Procedure
1 View the light from the discharge tube containing hydrogen using the
direct vision spectroscope.
2 A number of coloured lines against a dark background should
be seen.

Spectral series
Late in the nineteenth century, it was discovered that the wavelengths
present in the hydrogen spectrum fall into definite sets, called spectral
series. The Swiss physicist Johann Balmer discovered the first of these
series in 1885, when studying the visible region of the hydrogen spectrum.
The Balmer series contains all of the lines in the visible region of the
hydrogen spectrum.

Absorption spectra

The absorption spectrum of an element is the spectrum that is observed

after white light has been passed through the element.

An absorption spectrum of an element consists of a series of dark lines

against a coloured background. These dark lines are at exactly the same
wavelengths as the coloured lines in the emission spectrum of the element.

bine spectra as evidence for energy levels

The fact that only definite frequencies of light are emitted by hydrogen
atoms gives strong experimental evidence that the electron in the hydrogen
atom is restricted to definite energy levels. The Bohr theory accounts for the
line spectrum of the hydrogen atom as follows:

Under normal circumstances, the hydrogen electron is in the n = 1 energy

level, the ground state for the hydrogen atom. If the electron receives
enough energy it moves to the n= 2 energy level, which is an excited state
for the hydrogen atom. An electron in this state, being relatively unstable,
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

will eventually drop back to the ground state (Fig. 4.5), emitting energy
equal to the difference between the energies of the n = 2 and n= 1 energy
levels.

(kJ)
Energy
—>

Fig. 4.5

As a result, a line is obtained in the spectrum in the ultraviolet region.

The ground state electron may receive enough energy to be excited to the
n = 3 level. This electron in the n = 3 energy level need not necessarily
drop back directly to the ground state. Instead, it can drop to the n = 2
energy level, emitting light of a particular wavelength in the visible
region. This line is one of the Balmer series. All of the lines in the Balmer.
series are due to electrons dropping from higher levels to the n = 2 energy
level.

Other elements and energy levels

For plement: ores than layileeneen, egtonline to veh Batis —— the
number of electrons that could be accommodated in an energy level could
not exceed 2n?.

Table 4.4 Number of electrons in energy levels

 ELECTRONIC STRUCTUREOFATOMS
The line spectra of elements other than hydrogen may be explained in terms
of energy levels as follows:

Electrons in an atom are restricted to particular energy levels. They receive

sufficient energy in a flame or in a discharge tube to move to higher energy
levels. They are now unstable, and rapidly fall to lower levels. Each time
they do this, they emit light of adefinite wavelength, whose energy is equal
to the energy difference between the two levels. This light appears as one of
the lines in the line spectrum of the element.

The line spectrum of each element is unique to that element because atoms
of each element have a different arrangement of energy levels and this gives
rise to different electronic transitions.

Atomic orbitals
In 1923, the French physicist Louis de Broglie stated that electrons, like
light, have the properties of waves as well as of particles.

There is considerable uncertainty about the location of an electron in an

atom at any given time. In 1927, Werner Heisenberg stated his
Uncertainty Principle.

The Heisenberg Uncertainty Principle states that it is not possible to

determine at the same time the exact position and velocity of an electron.

Because of the uncertainty about the exact location of an electron in an

atom, at any particular time, it is more meaningful to refer to the
probability of finding the electron in a particular position within the atom.
In calculating this probability, use is made of the fact that the electron has
a wave nature.

An atomic orbital is defined as a region in space where the

probability of finding an electron is relatively high.

Fig. 4.6 s orbital Fig. 4.7 p orbital

@)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Types of orbitals
There are a number of different types ‘of see Sie aresaad
(Fig. 4.6); p orbitals have a dumb-bell shape (Fig. 4.7); d orbitals and
f orbitals have more complex shapes. All orbitals can hold two electrons.

Table 4.5 Shape and orientation of orbitals

Energy level — Orbital Shape) ie)

n=4 1s Spherical
neZ 2s Spherical
2D. 2Py and 2p, Dumb-bell At right angles to
each other

nes 35 Spherical
3P,, 3P, and 3p, Dumb-bell At right angles to

Five 3d orbitals Seen les

n=4 As Spherical
4p,, 4p, and 4p, Dumb-bell At right angles to
each other
Five 4d orbitals
Seven 4f orbitals

Electronic configurations of atoms

A group of orbitals that all have the same energy is called an energy
sublevel. For example, the 2p,, 2p, and 2p, orbitals make up the 2p
sublevel, while the five 3d orbitals make up the 3d sublevel. Different types
of sublevel have different capacities, as shown in Table 4.6.

An energy sublevel is a group of atomic orbitals that all

have the same energy.

Table 4.6 Sublevels and their capacities

2s 2
2p 6
3s 2
3p 6
3d 10
As 2
Ap 6
 ELECTRONIC STRUCTURE OF ATOMS

To find out how electrons are arranged in different kinds of atoms, a diagram
such as Fig. 4.8 may be used. Electrons are assigned to the various sublevels,
using the Aufbau Principle.

Remember...
The 3d sublevel is of higher energy than the 4s sublevel.

4p
4s

3p
3s

2p
Energy
—> 2s

1s

Fig. 4.8 Order of filling in energy sublevels

In working out the electronic configuration of an atom, electrons are

allocated to the sublevel of lowest energy until this is full. Then electrons
are placed in the sublevel of next lowest energy, and the process is repeated
until all of the electrons are accounted for.

The Aufbau Principle states that electrons will occupy

the lowest energy sublevel available.

Example 4.1
? What is the electronic configuration of sodium?

Answer
Sodium has 11 electrons. Using the order of filling energy sublevels shown in
Fig. 4.8, the electronic configuration of sodium is 1572s*2p°3s'.

All elements in Groups I and II of the periodic table have the outermost
electrons in their atoms occupying an s sublevel. Hence this region of the
periodic table is referred to as the s-block.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 4.2
“/
4
Se
~ What is the electronic configuration of chlorine?

Answer
Chlorine has 17 electrons. Using the order of filling energy sublevels shown
in Fig. 4.8, the electronic.configuration of chlorine is 1s#2s?2p°3s*3p?.

Chlorine can be referred to as a p-block element. This is because, like all

elements that are members of one of the following groups in the periodic
table: Ill, IV, V, VI, VII and 0, it has the outermost electrons in its atoms
occupying a p sublevel.

7< Example 4.3

What is the electronic configuration of nickel?

Answer
Nickel has 28 electrons. Using the order of filling energy sublevels shown in
Fig. 4.8, the electronic configuration of nickel is 1s22s*2p°3s?3p°4s?3d®.

This approach to working out electronic configurations works for all but
two of the first 36 elements. The electronic configurations of two of the
d-block elements are exceptional, as indicated in Table 4.7.

Table 4.7 Electronic configurations of d-block elements

+ Element © Actual electron configuration —

Copper 1822572p0°3s230°4s'3d'0
Chromium — 1s22s?2p®3s*3p%4s'3d5

These unexpected configurations are due to the extra stability, in the case
of chromium of a structure with half-filled 3d and 4s sublevels, and in the
case of copper of a structure with a full 3d and a half-filled 4s sublevel.

Electronic configurations of ions

/

The electronic configurations of ions of s-block and p-block elements are

worked out in a similar way to that used for the electronic configuration of
atoms.
 a ELECTRONIC STRUCTURE: OFATOMS

Example 4.4
4 What is the electronic configuration of Ca2+?
4 \

Answer
A calcium atom has 20 electrons. This means that a calcium ion (Ca2+) has
18 electrons. The electronic configuration of Ca2* is 1s22s22p®3s23p°.

Example 4.5
~~< What is the electronic configuration of F-?

Answer
A:fluorine atom has 9 electrons. This means that a fluoride ion (F-) has
10 electrons. The electronic configuration of Fis 1s#2s#2p°.

SSLSSHOSSHHOEAOKASEHHOSHRER
HT HROHKOSRHERE

2s 2D 2py Noy:
Carbon Itt it |Pe

Nitrogen td] It |

Oxygen ty] itt| It] it |It|

Fig. 4.9 The arrangement of electrons in orbitals in carbon,

nitrogen and oxygen

Electrons tend to occupy orbitals of equal energy singly where possible, as

in the cases of carbon and nitrogen. In an atom such as the oxygen atom,
pairing is necessary in the 2p, orbital, but the other 2p electrons occupy
the 2p, and 2p, orbitals singly, instead of occupying the same orbital.

Example 4.6
“What is the arrangement of electrons in individual orbitals in a silicon atom?

Answer
Silicon has 14 electrons. Using the order of filling energy sublevels shown in
Fig. 4.8, the electronic configuration of silicon is 1572s*2p°3s?3p?.

Each 2p orbital is full, and so the 2p electrons are arranged as follows:

2p 72p,/2p, In the 3p sublevel, there are two electrons available. These
occupy the 3p, and the 3p, respectively: Soe

Thus, the expanded electronic configuration of silicon is

2
1252p. pe
2p,/°2P, Eo, ee 3p, eee.
OE 38°3p;
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Atomic radii

The atomic radius of an element is defined as half the distance

between the nuclei of two atoms of the element that are joined ©
together by a single covalent bond.

———
| Bond |
| length !

Fig. 4.10 The atomic radius is equal to half the distance

between the nuclei of the two atoms

The size of the atomic radius of an element-depends on nuclear charge,

number of energy levels used, and the screening effect of inner electrons.

The atomic radius decreases on going from left to right across a period,
because of the increasing nuclear charge.

The atomic radius increases on going down a group, because of the addition
of extra filled energy levels, and the resultant extra screening by inner levels.

ee ~~ n=1 level oie agli

ee \ q , “ast °
‘ee, \ 8 EC ~ \ ‘n= level
i,Wm { = Pol at
a; Vath i 1 i 4
\ \ / j : \ a) rst
\ Ne vf / t oe
le
ee NE
oe a\
,
:
pa
-
3 Se ue gs 7 n=2 level”
Lithium ae

Sodium

Fig. 4.11 The outer electron in a lithium atom is screened by electrons in

the n= 1 energy level only. The outer electron in the sodium atom is screened
by electrons in both the n= 1 and n = 2 energy levels

fonisation energies
The first ionisation energy of an element is defined as the
minimum energy required to remove the most loosely bound
electron from an isolated atom in its ground state.

+ =
Xa) > xX o e
 _ ELECTRONIC STRUCTUREOFATOMS

ef A
p=
“ eeecad
Fig. 4.12 Table of first ionisation energy values for the first 36 elements

The first ionisation energy of an element is measured in kilojoules per mole.

The first ionisation energy values generally increase on going from left to
right across a period in the periodic table, because of the increase in nuclear
charge and the decrease in atomic radius.

On going down a group, the values of the first ionisation energies decrease.
This is due to the increase in atomic radius, which makes it easier to remove
an electron from an atom despite the increased nuclear charge, and to the
screening effect of inner energy levels.

On going across the second period from left to right, first ionisation energy
values generally increase. However, beryllium (electronic configuration
1s?2s*) has a higher first ionisation energy value than the next element,
boron (ls? 2st 2pic) The beryllium atom, having a full outer sublevel, is
particularly stable.

Another exception in the second period to the general trend occurs between
nitrogen and oxygen. The first ionisation energy of nitrogen (electronic
configuration Is?2s*2p,)2p,12p 1) is greater than that of oxygen (electronic
configuration 1s?2s*2p,?2p,'2p,)). The nitrogen atom, having a half-full
outer sublevel, is particularly stable.

fonisation energies and energy levels

The second ionisation energy is the energy required to

remove the most loosely bound electron from each singly
charged positive ion in a mole of these ions.

+ 2+
ac’ @t &-
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

When all of the successive ionisation energy values for an element, for
example magnesium, are measured, it is found that the first ionisation
energy is less than the second ionisation energy, which in turn is less than
the third ionisation energy, and so on. This trend is due to the increasing
positive charge and decreasing radius of the species losing the electron.

The values do not increase in a regular manner, however, and this gives
evidence for the existence of energy levels in the magnesium atom.

Magnesium
The magnesium atom has 12 electrons, with 2 in the n = 3 level, 8 in the
n= 2 level, and 2 in the n= 1 level. There is a very large difference between
the second ionisation energy, when the second electron is removed from the
outer (n = 3) level, and the third ionisation energy, when the third electron
is removed from an inner level (n = 2). A similar ‘jump’ occurs between the
10th ionisation energy, where the electron is in the n= 2 level, and the 11th
ionisation energy, where the electron removed is-in the n= 1 level.

The periodic table and electronic structure

The alkali metals.
The Group I elements in the periodic table — the alkali metals — all have
similar chemical properties because they have similar outer electronic
configurations. The radii of the atoms of these elements increase, with the
addition of extra energy levels, and consequent extra screening, on going
down the group. As a result, the outermost electron is more loosely held and
more easily removed, leading to increased reactivity.

This is why potassium is more reactive than sodium, which in turn.is more
reactive than lithium.

a { | } | { {

Le BL TS o
Lithium es awe z eee /
sue 5) ce

Potassium

Fig. 4.13 The reactivity of an alkali metal atom increases as the

size of the atom increases
 __ ELECTRONIC STRUCTURE OF ATOMS

The Group VII elements, the halogens, very often gain electrons in their
reactions. The halogens have similar chemical properties because of their
similar outer electronic configurations. Halogen atoms increase in radius on
going down the group, with an increase in the number of energy levels and
resulting extra screening. Their ability to gain electrons diminishes
accordingly. This is why bromine is less reactive than chlorine, which in
turn is less reactive than fluorine.

ea te bata Haig
i . \ i] j j

— \ 3 S. / / @ \ \
\

Fluorine \ aces a, Py em, é /

aNSe —— 9 nthoo” am x* . Me . ee «coaloo /
: an Ne a
. ~
Chlorine ‘o.. a a
Bromine

Fig. 4.14 The reactivity of a halogen atom decreases as the

size of the atom increases

In general, elements in the same group of the periodic table have similar
chemical properties because they have similar outer electronic configurations.

Key Points
~ An energy level is a region of definite energy within the atom that
electrons can occupy.
A line spectrum is a series of coloured lines against a dark background.
The absorption spectrum of an element is the spectrum that is observed
after white light has been passed through the element.
The Heisenberg Uncertainty Principle states that it is not possible to
determine at the same time the exact position and velocity of an electron.
An atomic orbital is a region in space where the probability of finding an
electron is relatively high.
_ An energy sublevel is a group of atomic orbitals that all have the same
energy.
The Aufbau Principle states that electrons will occupy the lowest energy
sublevel available.
(continued)
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

@ The atomic radius of an element is defined as half the distance between the
nuclei of two atoms of the element that are joined together by a single
covalent bond.
@ The first ionisation energy of an element is defined as the minimum energy
required to remove the most loosely bound electron from an isolated atom
in its ground state.
e@ The second ionisation energy is the energy required-to remove the most
loosely bound electron from each singly charged positive ion in a mole of
these ions.

Sample Question
2007, Hl, Question 5(a)
(a) Define energy level. (5)
Write the electron configuration (s, p) for the sulfur atom in its ground
state, showing the arrangement in atomic orbitals of the highest energy
electrons. é (6)

State how many (/) energy levels, (i/) orbitals, are occupied in a sulfur
atom in its ground state. (6)

Your revision notes

(40)
 CHAPTER 5
Oxidation and Reduction

@@ © Topics Covered in this Chapter

Oxidation and reduction in terms of loss and gain of electrons
Oxidising and reducing agents
Redox reactions of Group VII elements
The electrochemical series
Electrolysis
Electrolysis demonstrations
Electroplating

Oxidation and reduction

Oxidation is the loss of electrons.

In an oxidation—reduction reaction (redox reaction) there is a transfer of

electrons from one chemical species to another. In redox reactions, both
oxidation, or loss of electrons, and reduction, or gain of electrons, occur.
-A chemical species is said to be oxidised if it loses electrons, for example
Zn in the reaction
2+ 2+
ZN.) + Cu eat? Zn faa Cuc,
aq

while it is reduced if it gains electrons, for example Cu~* in the above reaction.

Reduction is the gain of electrons.

Burning, rusting and the browning of apples are everyday examples of redox
reactions. :

Rusting of iron
In the rusting of iron, iron reacts with oxygen and water, forming first Fe**
ions and eventually Fe* ions. In this reaction, the iron atoms lose electrons
and are oxidised. Oxygen atoms gain electrons and are reduced.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

In reactions such as

2Nay + Clyg) > 2NaCl.

metals are oxidised when forming compounds, since they form positive ions
and therefore lose electrons. In the above example, the metal sodium loses
electrons and is oxidised. The non-metal chlorine gains electrons and 1s
reduced.

Example 5.1 ;
What is oxidised and what is reduced in the following reaction?
2Ca. + Org) > 2CaO0,,

Answer
Calcium on reacting with oxygen forms positive ions by losing electrons, and
is oxidised. Oxygen gains electrons from calcium and is reduced.

In a reaction such as

2NaCl,. => 2Na,,) 4. Clog)

sodium ions in sodium chloride gain electrons to form sodium atoms, and
are therefore reduced. Chloride ions lose electrons to form chlorine
molecules and are oxidised.

Example 5.2
What is oxidised and what is reduced in the following reaction?
ZNSO gag) + MQ. — ZN) + MgSO 434) sgt

Answer .
Magnesium on reacting forms positive ions by losing electrons and is oxidised.
Zinc gains electrons from magnesium and is reduced.

Oxidising and reducing agents

The oxidising agent is itself reduced in the reaction. For example, in the
reaction
24 De
Cu (aq) wt Mg) = Cu, iv Mg (aq)

copper, which is itself reduced, is the oxidising agent.

 OXIDATION AND REDUCTION |
Swimming pool water treatment
Water in swimming pools is kept in good condition through adding oxidising
agents that kill microorganisms by oxidising them. Chlorine or compounds of
chlorine such as sodium hypochlorite are used. When either of these
substances is added to water, the oxidising agent HOCI is formed. When this
acts as an oxidising agent, it is reduced to the chloride ion (CI).

An oxidising agent is a substance that allows oxidation to happen

by gaining electrons itself.

A reducing agent is a substance that allows reduction to happen

by losing electrons itself.

The reducing agent is itself oxidised in the reaction. For example, in the
reaction

Cu 2+
Boe: Mg.) —> (a.
Cu +t Mg 2+
ed

magnesium, which is itself oxidised, is the reducing agent.

Example 5.3
What is (i) the oxidising agent and (ii) the reducing agent in the following
reaction?

Zn 2 ven + Cay —> ZN) + Ca 2 Be)

Answer
(i) Since zinc gains electrons in the reaction, it is reduced and therefore is the
oxidising agent.
(ii) Since calcium loses electrons in the reaction, it is oxidised and therefore is
the reducing agent.

Redox reactions in Group Vil elements

The Group VII elements can all act as oxidising agents, oxidising, for
example, solutions containing sulfite ions or iron(II) ions. Chlorine is a
more powerful oxidising agent than bromine, which in turn is more
powerful than iodine.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Mandatory Experiment 5.2(a): Redox reactions

of the halogens
(i) Reactions with halides
Chlorine oxidises bromide and iodide to bromine a ane ooecioek
aes 4 2Br= a VEE gar Br o(aq)
Clovaq) + 2) Ga => ACV aa) +: lbiaq)

Bromine can release iodine from a solution of its salts:

Bra (aq) + rd er _ ZT aa) + |(aq)

Procedure
1 Add 2 cm? of a chlorine solution and a sodium bromide solution,
respectively, to separate test tubes and mix. An orange colour should
appear, indicating that bromine has been formed.
2 Add 2 cm)? of a chlorine solution and a potassium iodide solution,
respectively, to separate test tubes and mix. A reddish-brown colour
should appear, indicating that iodine has been formed.
3 Add 2 cm? of a bromine solution and a potassium iodide solution,
respectively, to Separate test tubes and mix. A reddish-brown colour
should appear, indicating that iodine has been formed.

(ii) Reactions with iron(II) salts and with sulfttes

Solutions of chlorine, bromine and iodine are all able to oxidise iron(II) ions
to iron(II) ions, and to oxidise sulfite ions to sulfate ions in aqueous
solution. They react with iron(II) ions as follows:

Gydeg Aer a _. 2 Mea va Zhe.

Brovaq) + sett,p> ZB ey SFOam
ear 2Fe2+ \> Dae a ZF eal -

They react with ashions as bee

Clytagy + SO3%aq + HpOp > 2Ch iggy + $04? Beene
Br, 650, q t 4,0, po CBs Bp ere ao ehtie

, Sek i + HO, => 20. ‘as Soh y+ 2H" aq

Procedure
1 Add 2 cm? of a chlorine solution and an iron(II) sulfate solution,
respectively, to separate test tubes and mix. Then add 10 drops of the
sodium hydroxide solution to the mixture. A greenish-brown precipitate
should form — this indicates the presence of Fe** ions.
2 Repeat using a bromine solution instead of a chlorine solution. A greenish-
brown precipitate should form — this indicates the presence of Fe** ions.
 OXIDATION AND REDUCTION

3 Repeat using an iodine solution instead of a chlorine solution. A

greenish-brown precipitate should form — this indicates the presence of
Fe** ions.
4 Add 2 cm? of the chlorine solution and a sodium sulfite solution, :
respectively, to separate test tubes and mix. Using a dropping pipette,
add a few drops of barium chloride solution. Now add 2 cm? of dilute
hydrochloric acid. A white precipitate insoluble in the hydrochloric acid
should be observed — this indicates the presence of sulfate ions.
5) Repeat using a bromine solution instead ofa chlorine solution. A white
precipitate insoluble in the hydrochloric acid should be observed — this
indicates the presence of sulfate ions.
6 Repeat using an iodine solution instead of a chlorine solution. A white
precipitate insoluble in the hydrochloric acid should be observed — this
indicates the presence of sulfate ions.

The decrease in oxidising power of the halogens on going down the group
is due in part to the increase in atomic radius. This makes it more difficult
for the atom to gain electrons. The extra screening caused by the addition
of extra energy levels is another factor that has the same effect.

The electrochemical series

In the electrochemical series the metals are arranged in order of tendency
to lose electrons. The higher a metal is in the electrochemical series, the
more reactive it 1s.

Potassium
Calcium
Sodium
‘Magnesium
‘Aluminium
Zinc
tron
Tin
Lead
tendency
electrons
lose
to
ig
Hydrogen
Copper
Silver /
Gold
Fig. 5.1 The electrochemical series

Displacement of metals
A metal will displ a ie reactive petal, that is, one which is below it in
the electrochemical series, from a solution of its salts. The more reactive
me
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

metal is oxidised, and the less reactive metal is reduced. For example, if
magnesium ribbon is dipped in copper sulfate solution, it becomes coated
with copper, as the following reaction occurs:

Mg) + CUSOgag) > MGSOxaq) + CU)

The magnesium is oxidised and the copper is reduced. The further apart
metals are in the electrochemical series, the more readily will this type of
displacement reaction occur.

Applications of displacement reactions

An application of this type of reaction is the use of a less valuable metal — scrap
iron — to displace a more valuable and less reactive metal, copper, from a
solution of its salts:

Fe.) + CUSO g(a) -» FeSO4(aq) + Cu.)

Mandatory Experiment 5.2(b): Displacement

reactions of metals
In this experiment, zinc and magnesium, respectively, are
reacted with a solution of copper(II) sulfate.
ZN) + CUSOg(aq) > ZNSOg(aq) + CU)

Mg) + CUSO gag) > MGSOya) + CU)

Procedure
1 Half fill two boiling tubes with acidified copper(I] sulfate solution.
2 Add the magnesium ribbon to the solution in one boiling tube. The
blue colour of the copper(II) sulfate solution should fade and a brownish
precipitate of copper metal should be seen. ;
3 Add the zinc powder to the solution in the other boiling tube. The blue
colour of the copper(I] sulfate solution should fade and a brownish
precipitate of copper metal should be seen. ~

Electrolysis
Electrolytes are substances that conduct electricity when dissolved in water
or when melted. Acids like hydrochloric acid, bases like sodium hydroxide,
and salts like sodium chloride are all electrolytes. Electrolytes are
chemically changed when an electric current is passed through them. This
process is called electrolysis.

Electrolysis is the use of electric current to cause a chemical reaction.

\ ee DLE Na OXIDATION AND REDUCTION

Oxidation occurs at the anode. Reduction occurs at the cathode.

Electron flow*|,|,~ Electron flow

Electrodes

Anode Cathode
(positive electrode) (negative electrode)

Fig. 5.2 What happens during an electrolysis

Specified Demonstration: Demonstration of

ionic movement cee
During electrolysis of a solution, positive ions (cations) are attracted to
the negative electrode (cathode) and negative ions (anions) are attracted
to the positive electrode (anode). The coloured ions in this demonstration are:

copper(II) [Cay — blue

chromate(VI) [CrOF aqyt — yellow

Procedure
1 Add urea to a solution of copper(II) chromate in 2 M hydrochloric acid.
‘This is done to increase the density of the solution.
2 Add the resulting solution to a U-tube until it is about half full.
3, Add 2 M hydrochloric acid to each arm of the U-tube, taking care to
avoid mixing the layers.
4 Complete setting up the apparatus as shown in the diagram.

Carbon electrodes

Dilute hydrochloric acid

Copper(II) chromate solution

U-tube

Fig. 5.3
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

5 The blue copper(II) ions should be observed moving towards the

cathode, and at the same time the yellow chromate(VI) ions move
towards the anode.

Electrolysis demonstrations
Electrolysis of aqueous solutions
In the electrolysis of copper(II) sulfate solution using copper electrodes, copper
at the anode is oxidised and dissolves, and copper is formed at the cathode.

Electrolysis of aqueous copper(II) sulfate solution using copper

electrodes
At the anode, copper is oxidised:

SU ie UC aya Ze

At the cathode, copper is reduced:

2 sy
Gil aa +2e > Cur.

In the electrolysis of acidified water using inert electrodes, oxygen gas is

formed-at the anode and hydrogen gas is formed at the cathode.

Electrolysis of acidified water

Dilute sulfuric
acid solution

Platinum Platinum
electrode electrode

Switch

eee
Fig. 5.4 Electrolysis of acidified water using a voltameter
 OXIDATION
AND REDUCTION —

At the anode, water is oxidised:

H50,) = a aa) + 2204) + 2e-

At the cathode, Ht ions are reduced:

2H feqyer 2e > Hq)

+ —

Specified Demonstration: Electrolysis of aqueous

Sodium sulfate solution using universal indicator
In the electrolysis of sodium sulfate solution using inert electrodes, oxygen
gas is formed at the anode, and hydrogen gas is formed at the cathode. At
the cathode, molecules of water are reduced, according to the equation:
2H,0q + 2€° > Ha4 + 20H.)

At the anode, molecules of water are oxidised, according to the equation:

H,0y > Dthetag) a 2204) 20s

Procedure
1 Add about 2 cm? of universal indicator solution to 250 cm? ssadinimn
sulfate solution. Stir well and fill the voltameter with this solution.
2 Switch on the power supply, and increase the voltage to 10 V.
3 The green colour of the indicator should turn blue at the cathode,
because of the alkaline solution formed there, and red at the anode
because of the acidic solution formed there.

Specified Demonstration: Electrolysis of aqueous

potassium iodide using phenolphthalein indicator
In the electrolysis of potassium iodide solution using inert electrodes,
iodine is formed at the anode, and hydrogen gas is formed at the cathode.
At the cathode, molecules of water are reduced, according to the
equation:

2 2H,0W) + 2e => Ho(9) + 20H (aq)

At the anode, the I” ions are oxidised, according to the equation:

Ze > l(s) + 20>

Procedure
CROSS HEROS HSH FTHRESHRSHSHESHSSEHRESSSSESOHESHSHEHESEHERHEOHRAEHE

i-eAdd abode 10 drops ofphenolonralern Plicacortto 250 cm? potassium

iodide solution. Stir well and fill the voltameter with this solution.
2 Switch on the power supply and increase the voltage to 10 V.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

3 A pink colour should be observed at the cathode, because of the alkaline

solution formed there. A brown colour at the anode shows that iodine is
formed there.

Electroplating
In electroplating, a layer of a metal is put onto the surface of another metal.
Cutlery made of nickel can be coated with silver by electroplating. This
increases the value of the cutlery and improves its appearance.
dc power
supply

Silver nitrate
electrolyte

Spoon being Silver

electroplated anode

Fig. 5.5 Arrangement for plating a spoon with silver

Another example of electroplating is the coating of steel with chromium to

improve its appearance and resistance to corrosion.

Electroplating is the coating of a metal onto the surface of another

metal using electrolysis.

Copper is purified using impure copper as an anode and pure copper as a

cathode, with acidified copper(II) sulfate used as the electrolyte. —

Impure copper Pure copper

anode cathode

Acidified copper
sulfate solution

Impurities

Fig. 5.6 Arrangement for purifying copper

 OXIDATION AND REDUCTION
Table 5.1

a pplications of‘electroplating _
~ Chromium- “plating of steel
Silver-plating of nickel (cutlery)
Purification of copper

@ Oxidation is the loss of electrons.

@ Reduction is the gain of electrons.
An oxidising agent is a substance that allows a to happen by
gaining electrons itself. :
A reducing agent is a substance that allows reduction to happen by ose
_ electrons itself.
Electrolysis is the use of electric current to cause a chemical reaction.
Electroplating is the coating of a metal onto the surface of another metal
using electrolysis.

Sample Question
2008, Hl, Section B, Question 10(b)
COPS EOS SET OH SHO SHLEHH HSE OEE THEHETEH SCH DOHE CHO PHETE
TOWEL UES HO SHON HEHE PP SED A GD Oe BA SB Woo!

(b) Define oxidation in terms of (/) electron transfer, (//) change iin
oxidation number. 7):
Mil) For the redox reactions shown below, use oxidation numbers.
to identify the species oxidised in the first reaction and the
oxidising reagent in the second reaction. (6)

clo-+F+Ht > CF+1,+H,O

I, +$,0,77° > £+5S,0,%
Using oxidation numbers or otherwise balance both
equations.
 CHAPTER 6
fonic and Covalent Bonding

@®® Topics Covered in this Chapter

Chemical compounds
Noble gas electron configuration
Octet rule and exceptions
Valency
Ionic bonding
Tonic crystal structure
Characteristics of ionic substances
Tests for anions
Covalent bonding
Double and triple covalent bonds
Polar and non-polar covalent bonding
Characteristics of covalent substances
Electronegativity

Chemical compounds
A compound is formed when two or more elements combine in a chemical
reaction. For example, if hydrogen gas is burned in oxygen gas, the
compound water is formed.
2H5¢9) + Oo) > 2H,0y

Unlike elements, compounds can be broken down chemically into simpler

substances, and ultimately to their elements.

Each compound has a fixed composition and it can be represented by a

chemical formula, e.g. H,O.

Hydrated substances contain molecules of water in definite proportions,

usually locked into a crystal structure. Washing soda (hydrated sodium
carbonate) is one example. It contains 10 parts of water to one part of
sodium carbonate, so its formula is Na,CO,-10H,O.
a NONICAND COVALENT BONDING (OE
Water bound in this way is described as water of crystallisation. It can
be driven off by heating to give the corresponding anhydrous
compound.

Na,CO;10H,O,) > Na,CO,,) + 10H,O. S

Noble gas electron configuration

The elements of Group 0 of the periodic table, the noble gases, are
found to be very stable and unreactive compared with most other
elements. This is due to the stability of their outer electronic
configurations.

The uses of helium and argon are related to their chemical unreactivity.
@® Helium is used in weather balloons and blimps, because it has a very
low density, but unlike hydrogen it is not flammable.
@ Electric light bulbs are filled with argon to prevent the tungsten
filament from evaporating or reacting.

Table 6.1 shows the distribution of electrons in the main energy levels of
noble gas atoms.

Table 6.1

Peel sey in we,

Neon (Ne) 2,8
Argon (Ar) 2/88
Krypton (Kr) 2,8, 18; 8

ir Poe aie
- : f
re,
ae ‘ f
o f 2 ~~O~. o. \ \,
y <es, ah, Se, Sa
f( ; o 7{ \ 8| / ? ff \| 8| \|
|\ WE ee) 4a , @) rs
i |

a A ee } j ee
7 Af 5 x rs fg \ Q \ Pai yd i

ie cl be geal a gol Ane

Helium betes nity 3 og
Neon ‘iar
Argon

Fig. 6.1

Apart from helium, whose outer level (and only occupied level) needs just two
electrons to be filled, eachof the other noble gases has eight electrons — an
octet — in its outer level. (53)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Given the relative unreactivity of the elements, it is clear that having eight
electrons in the outer level, or having a filled outer level, is a stable
arrangement of electrons.

Octet rule and exceptions

The octet rule states that atoms on reaction tend to reach an electron
arrangement with eight electrons in the outermost energy level. Elements
achieve these stable noble gas configurations by losing, gaining or sharing
electrons when they react to form compounds.

For example, in the formation of sodium chloride from sodium, the sodium
atom, whose electron arrangement is 2, 8, 1, loses an electron to chlorine,
ending up as the sodium ion Na* with an arrangement of 2, 8.

On the other hand, chlorine gains an electron from sodium and its electron
arrangement goes from 2, 8, 7 in the neutral atom to 2, 8, 8 in the chloride
ion. In other words, both elements obey the octet rule and end up with
eight electrons in the outer level.

While the octet rule does not work in all cases, it is nonetheless a
useful aid in using the electron structure of atoms to predict the ions
formed in ionic bonding and the consequent chemical formulas of
compounds.

Example 6.1
Use the octet rule and the electron structures of magnesium and bromine to
predict the formula of magnesium bromide.

Answer
The electronic structure of magnesium is: Mg 2, 8, 2
The electronic structure of bromine is: Br 2, 8, 18, 7

To obey the octet rule and end up with eight electrons in the outer level,
magnesium loses two electrons to form the magnesium ion Mg*, and
bromine gains one electron to form the bromide ion, Br-. So that the total
charge is zero, two bromine atoms are required, gaining one electron each.
Consequently, the formula of magnesium bromide is MgBr,.

A similar method is used to predict the formulas of compounds of complex

ions. It is not possible to use the octet rule to work out the charges on such
ions. The information required is shown in Table 6.2.
 _IONIC AND COVALENT BONDING —
Table 6.2 Formulas of complex ions

Hydroxide
Carbonate
Nitrate

Hydrogencarbonate
Sulfite
Sulfate

Example 6.2
What is the formula of sodium carbonate?

Answer
The electronic structure of sodium is: Na 2, 8, 1

The sodium ion is Na* and the carbonate ion is COR. Two sodium ions and
one carbonate ion are required so that the total charge is zero. Thus, the
formula is Na,CO,.

Exceptions to the octet rule

SOSSOHSHSSSSSETEESHHEEHESHOTHEEHERHEAREHHEHEEHEEHESOHHEHHOHTHTSASEHOESHROHHROTHHROEHRASEHREHOOSS

There are several exceptions to the octet ane.

1 Hydrogen, lithium, beryllium and boron tend to reach the electronic
structure of helium.
2 The d-block elements do not usually obey the octet rule.
3 The rule works in some cases for sulfur and phosphorous, but not in
others.

Valency
Valency gives a measure of the combining power of an atom.
»

The valency of an element is the number of bonds each atom

of the element forms when it reacts.

For example, carbon forms four bonds when it reacts, so it has a valency of 4.

The valency of an element can usually be worked out by calculating the

number of electrons that its atoms would need to lose or gain to attain a stable
electronic structure such as that of the nearest noble gas in the periodic table. (ss)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Table 6.3 Valencies of s-block and p-block elements

Group number Valency Group numbe

1 1 ) ile

2 Zax 6 Ms

5) 3 7 1
4 4 0 0 -

Transition elements have variable valencies, some of which are shown in

Table 6.4.

Table 6.4 Valencies of transition elements

Chromium 2530
Manganese DESMAN ON

lron 2356

Copper : tp 2

Example 6.3
What is the formula of water, a compound containing oxygen and hydrogen
only?

Answer
Oxygen has a valency of 2, while hydrogen has a valency of 1. An oxygen atom
will therefore form two bonds, and hydrogen will form one bond. Two
hydrogen atoms are therefore required to bond with one atom of oxygen.

H-—= (0

H
Fig. 6.2 :

Thus, the formula of water is H,0.

lonic bonding
When atoms combine together to form compounds, there is a change in the
arrangement of the electrons in the outermost energy level of each atom.
Some of these electrons form links called chemical bonds between the atoms.
Usually the new arrangement is more stable than the original situation.
 IONIC AND COVALENT BONDING
Tonic bonds are usually found in compounds that contain metals combined
with non-metals. The word ion is used to describe any species that has
unequal numbers of protons and electrons, and so carries an electric charge.
Like atoms, ions are extremely small.

Metals lose one or more electrons and become positively charged ions or
cations. A sodium ion (Na‘*) is formed when a sodium atom loses one
electron. The ion has an overall charge of+1 because it has 11 protons but
only 10 electrons. In terms of electron structure, the change is:

Na 2,8,1-1e
—>Na* 2,8

@ “ow \ C e
: \ oses era ae

toe- oe| e\|, 41e

'! \ | \ 7 electron ? / \ |

e
s \ eo
e e ‘ox. e

Sodium atom Sodium ion

Fig. 6.3

Non-metals gain one or more electrons and become negatively charged ions
or anions. A chloride ion (Cl-) is formed when a chlorine atom gains one
electron. The ion has an overall charge of —1 because it has 17 protons and
18 electrons. In terms of electron structure, the change is:

CU2-8 free =>. Cl 2-8-3

a’ a
Fad y
Sf we % P eo a
he a Ff pilin >
[Sf i. \_ Gains / of |
peti f \ 3 \ telectron {| [ / \\ 4
of{
\ fe) Ny
@ /
}}}——e
|| @ }} 9
3 / ‘ @ \ J 3 }

—~o~ / / oO
QR On... OG a Oe Se sg
women) a id O° a

Chlorine atom Chloride ion

»

Fig. 6.4

In order that an ionic bond can be formed, as between sodium and chlorine,
electrons are transferred from the metal atoms to the non-metal atoms
during the chemical reaction, forming ions.

An ionic bond is the electrostatic force of attraction between

oppositely charged ions.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 6.4
Draw a dot and cross diagram to show the formation of an ionic bond
between potassium and fluorine.

Answer

Ko + “Fe ——» [Kk]+ Fal

(2e8, 8; 1) eee (2,8,8) (2,8)
Potassium Fluorine Potassium Fluoride
atom atom ion ion

Fig. 6.5

The charges on the potassium and fluoride ions are equal but opposite. They
balance each other and the resulting formula of potassium fluoride is KF.

fonic crystal structure

In ionic bonding, the oppositely charged ions attract each other to form a
rigid three-dimensional lattice. Each ion in the lattice is surrounded by
others of opposite charge.

Fig. 6.6 Structure of sodium chloride

Figure 6.6 shows the structure of a small part of a single sodium chloride
crystal. Many millions of sodium and chloride ions are arranged in this way
in a single crystal of sodium chloride to make up a giant ionic structure. It
may be deduced that ions are extremely small in size.

In a NaCl crystal, each sodium ion in the lattice is surrounded by six

chloride ions, and each chloride ion is surrounded by six sodium ions.
However, not all ionic substances have the same crystalline structure as
sodium chloride.
 IONIC AND COVALENT BONDING

Characteristics of ionic Sobhtamces

@ Ionic substances have high melting points and high boiling points, and
are hard solids at room temperature.
@ They cannot conduct electricity in the solid state because the ions are
held tightly in the crystal and are not free to move.
@ Most ionic substances dissolve in water to some extent.
@ onic substances conduct electricity when molten or in aqueous
solution — they are electrolytes.

fonic materials in everyday life

SPHHOSHSSHEHHEHSSESHEOSH
OSHS HHHEHHETHHERTEHREROSHO SE STROSS SSHOKAHOHHHTEHR OSH SEH ESEKOHEOHEDHHHOCEBS

@ Salt tablets are taken to replace salt lost from the body. ie sweating.
* @ Brine, a solution of sodium chloride, has long been used for curing
bacon. This effectively is a preservation process.
@ Fluoridation of water supplies to prevent tooth decay is carried out by
adding a salt of fluorine such as sodium fluoride (NaF) or sodium
fluorosilicate (Na,SiF,).

Tests for anions

Mandatory Experiment 6.1: Tests for anions in
aqueous solutions: chloride (CI-), carbonate
(CO,?-), nitrate (NO,-), sulfate (S0,?-),
phosphate (P0,>-), sulfite ($0;7-),
hydrogencarbonate (HCO;~ )
(a) To test for the carbonate (CO,?~ ) and hydrogencarbonate
(HCO,-) anions
PHOS STESSSSSSHAERSSS SSE SESASHHHHSHOSHEOHH SHS SOSSESEHEOSOHRSOHHE SEES OEHRESHESHEHRHEHOHHOOHSESENRTE

Carbonate and Wh eee cantiesions both react with dilute Evroctiane

acid to produce carbon dioxide gas.
(i) NaHCO,,,,) + HCl aq) = NaCl.) + HO, ue CO5(4)

(ii) Na,CO3/29) + 2HCli2q) > 2NaCl., )+H, Oy et COx,

Hydrogencarbonate
si hee idea ah Lime |
water \_
hycrochioric acid

Fig. 6.7
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

To distinguish between carbonate and hydrogencarbonate ions, a solution

of magnesium sulfate is added. Since magnesium carbonate is insoluble in
water, a white precipitate indicates that the salt is a carbonate.
Na,CO, 3(aq) + MgSO qiaq) > Na SO 4/24) + MgCO3,.

The absence of a precipitate indicates a hydrogencarbonate because

magnesium hydrogencarbonate is soluble in water:

2NAHCO3.9q) + MGSO q¢aq) > Na2SOniaq + MG(HCO5)2(aq)

However, on heating this solution, a white precipitate is formed because
hydrogencarbonates decompose into carbonates on heating:
Mg(HCO3)or4q) > MGCOxq + H,Oy + CO,

(b) To test for the sulfite ($0.7) and sulfate ($0, ) anions
Both sulfite and sulfate ions react with. barium chloride solution,
producing white precipitates of barium sulfite and barium sulfate,
respectively.
(V) Na,5O
5499)+ BAClyj9¢) > ZNAC hag) + BASO3,6
(ii) Na,SOq(aq) 4 BaCl (aq) => 2NaCl(24) + BaSO A(s)

Barium sulfite reacts and dissolves in hydrochloric acid but barium sulfate
does not.

BaSO.,) + ZHCliaq) > BaClayqq) + HOw + SOz%9

This reaction is used to distinguish between sulfite and sulfate ions.

(c) Totest for the chloride (CI-) anion =

shar containing chloride ions react with silver nitrate solution,
producing a white precipitate of silver chloride.
NaCl (aq) + AGNO3,,) 3(aq) > NaNOx,,) 3(aq)
+ AC.)

This precipitate dissolves when dilute ammonia solution is added.

(d) To test for the nitrate (NO,-) anion

Solutions containing nitrate ions react with a mixture of iron(II) sulfate
solution and concentrated sulfuric acid. When concentrated sulfuric acid is
added to a mixture of nitrate and iron(II) sulfate solutions, a brown ring
develops slowly where the sulfuric acid layer and the layer containing the
mixture meet.
 IONIC AND COVALENT BONDING

wy
Nitrate solution and Addition of Brown ring indicates
iron(II) sulfate solution concentrated sulfuric acid presence of the nitrate ion

Fig. 6.8

(e) To test for the phosphate (PO,5-) anion

Solutions containing phosphate ions react on heating with an ammonium
molybdate reagent, forming a yellow precipitate. This precipitate dissolves
when ammonia solution is added.

Table 6.5 Tests and results for anions in aqueous solutions

om ag Test :
Carbonate and Add dilute HCI to Gas produced that turns
Hydrogencarbonate carbonate or lime water milky
yy hydrogencarbonate solution
Carbonate Add MgSO,,,.) to White precipitate
» carbonate solution
Hydrogencarbonate Add MgSO 4/44) tO White precipitate on
V hydrogencarbonate solution heating
Sulfate Add BaCl,,,,) to sulfate White precipitate that is
: Y,Y : Seles
solution insoluble in dilute HC!
solution
Sulfite WAEY
Add BaCl,,,,) q) to sulfite White precipitate
: 3
that is
“VY solution soluble in dilute HCI
solution
Chloride Vv Add AGNO3,,,) to White precipitate that is
chloride solution soluble in dilute NH,
x solution
Nitrate / Mix nitrate solution with Brown ring forms
V/ cold FeSO g(aq): Pour
concentrated H,SO, down
inside of test tube

Phosphate Add ammonium Yellow precipitate which

molybdate reagent and is soluble in ammonia
heat-gently solution
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Covalent bonding
When atoms combine chemically other than by ionic bonding, molecules are
formed. These may consist of atoms of the same element, such as the
hydrogen molecule (H,), or of atoms of different elements, such as the sulfuric
acid molecule (H,SO,). Molecules, like atoms, are extremely minute.

Atoms can gain the stability of the noble gas configuration by sharing
electron pairs in their outer levels. Each shared pair of electrons is regarded
as one covalent bond. Shared electrons count as part of the outer level of
both atoms of the bond.

A covalent bond is formed when two atoms share a

pair of electrons.

The simplest example of this type of bonding is the hydrogen molecule

(H,). A hydrogen atom has one electron. In order to obtain a full outer level
and gain the-electron structure of the nearest noble gas, each of two
hydrogen atoms share a pair of electrons, and a. covalent bond is formed.
Since there is just one shared pair of electrons, this is a single bond.

H* + .H —— H?H
Fig. 6.9

Example 6.5
Draw a dot and cross diagram of the fluorine molecule (F,).

Answer
The fluorine molecule (F,) is another example of a single covalent bond
between two atoms of the same element. .

rPX + °Fr > SF IF:

e

XX ee XX ee

Fig. 6.10
Since fluorine atoms have seven electrons in their outer lavels, this time the
octet rule is obeyed and each atom gains the electron structure of neon.

Example 6.6
Draw a dot and cross diagram of the hydrogen sulfide molecule (H,S).

Answer
Hydrogen sulfide is an example of a molecule with three atoms, where both
hydrogens are bonded to the sulfur.

(continued)
 |ONIC AND COVALENT BONDING

Fig. 6.11
Since the sulfur atom has six electrons in its outer level, it needs to gain two
electrons to reach the electronic structure of argon. It does this by sharing
electrons with each of two hydrogen atoms. The hydrogen atoms reach the
configuration of helium in the process. The resultant hydrogen sulfide molecule
has two single covalent bonds.

Shared electron pairs that form covalent bonds are called bond pairs. Pairs
of electrons not involved in bonding are called lone pairs or non-bonding
pairs. A hydrogen sulfide molecule has two bond pairs of electrons and two
lone pairs of electrons.
H 3S:
H
Fig. 6.12

Double and triple covalent bonds

Some atoms form covalent bonds by sharing two or three pairs of electrons.
An example of a molecule with two shared pairs is the oxygen molecule (O,).
Since an oxygen atom has six electrons in the outer level, it needs to gain two
electrons, or a share of two electrons, to reach the electron structure of neon.
Two oxygen atoms share two pairs of electrons to reach the octet.

Example 6.7
Draw a dot and cross diagram of the oxygen molecule (O,).

Answer

OO @

Fig. 6.13
A double covalent bond is formed in which two pairs of electrons are shared.

The double bond in the oxygen molecule can also be represented as O = O.

When three electron pairs are shared to form a bond, a triple covalent bond
is formed. The nitrogen molecule is an example in which this type of
bonding is found. Since a nitrogen atom has five electrons in the outer level,
it needs to gain a share of three more electrons to reach the electron structure
of neon. Two nitrogen atoms share three electrons each to reach the octet.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 6.8
Draw a dot and cross diagram of the nitrogen molecule (N,).

Answer :
oN ox Nx

Fig. 6.14

A triple covalent bond is formed in which three pairs of electron are shared.

The triple bond in the nitrogen molecule can also be represented as N=N.

A single covalent bond between two atoms is called a 6 (sigma) bond. A

oO bond is always formed between two atoms in a molecule if they are
covalently bonded.

Overlapping p orbitals Molecular orbital

Fig. 6.15 Sigma bonding by end-on overlap of p orbitals

A sigma bond is a covalent bond between two atoms formed

by end-on overlap of orbitals.

In double or triple bonds, sideways overlap is possible between two p atomic

orbitals, each containing one electron. In this case, a 2 (pi) bond is formed.

Fig. 6.16 Pi bonding between two p orbitals

A pi bond is a covalent bond between two atoms formed by

sideways overlap of orbitals.

An example of a t bond is found in the oxygen molecule (O,). The O= O

double bond, like all double bonds, consists of one o bond and one bond.
Triple bonds, such as that in the nitrogen molecule (N = N), consist of one
oO bond and two 7 bonds. Of the two types of covalent bond, o bonds are
stronger.
 __IONIC AND COVALENT BONDING _
Polarstenon-easier covatiat sainihag
Molecules such as hydrogen (H,), oxygen (O,5), nitrogen (N, ), chlorine
(CL,) and bromine (Br,) each contain only one type of atom. Gueenencly.
ines nuclei of the atoms attract the shared electrons in the covalent bond
equally. The bond is a pure covalent bond and is said to be non-polar.

However, most covalent bonds are formed between atoms that are quite
different from each other.

Usually, different types of atoms will attract the electrons unequally in a

covalent bond. The atom with the lesser share of electrons will become
slightly positively charged, indicated by 6+, and the other atom will
become slightly negatively charged, indicated by O-. In the hydrogen
chloride molecule (HCl) for example, the chlorine atom has a greater
attraction for the shared pair of electrons than the hydrogen atom.
Consequently, the molecule is represented as follows:
Ho+ ae (los

A polar covalent bond is a covalent bond in which there is

unequal sharing of electrons.

Specified Demonstration: Polarity test for

liquids using a charged plastic rod
If a liquid contains polar molecules, a flow of that liquid from a burette
will be attracted to a charged polythene rod, resulting in the flow bending.

Procedure —
‘Add 25 cm 3 of the end fader igen toaA eed Mies:
Place a beaker under the jet.
Charge the polythene rod with the cloth by rubbing it.
Open the burette tap and allow the liquid to run into the beaker.
Bring the charged rod close to the liquid stream.
FE If the liquid is polar, the liquid stream bends towards the rod.
KR
NA
ON
WN

Characteristics of covalent substances

® Most covalent substances are liquids or gases at room temperature.
Those that are solids have low melting and boiling points.
® In general they do not conduct electricity when molten or in solution.
However, some molecules such as HCl react with water to form ions
and the solution formed can then conduct electricity.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

® Most covalent substances do not dissolve readily in water. However,

many covalent compounds have some ionic character — they are polar
covalent — and these are more likely to form aqueous solutions.

Polar and non-polar materials in everyday life ve et inae

Table 6.6

oo Norepelan
‘Water (for washing clothes) Cooking oil
Glucose (in Lucozade) Petrol

Mandatory Experiment 6.2: Recrystallisation

of benzoic acid and determination of its
melting point

(a) Recrystallisation
An impure solid may be purified by recrystallisation.
Procedure
1 Flute a filter paper, place it in a
funnel, and keep it warm and Beaker
moist by standing it over a source
of steam.
2 Place about 1 g of the impure Filter funnel
benzoic acid sample in a small fluted filterpaper
beaker and dissolve it in the
minimum amount of boiling
water.
3 Pour the boiling solution through Conical flask
the filter paper in small portions,
collecting the filtrate in a warm
conical flask. If any crystals form
in the filter paper, add a little
boiling water to dissolve them. as Bil7
4 Transfer the filtrate to a warm beaker, and evaporate off the water until
traces of crystals begin to appear on the sides of the beaker. Allow the
filtrate to cool to room temperature.
WN" Carefully filter the recrystallised mixture, by vacuum filtration if possible.
6 Wash the crystals with small portions of ice-cold deionised water and
allow to dry.
— : IONIC AND COVALENT BONDING

(b) MeltingAte eaeniation

SHSHSHSHOSHSSERTSHSESHEHSHESHHEHSEHEHHEEHOHEEHTSHESHTHSHEEHREOHHHEHOTEOEHEHSEHOHERHHEOHEOHTOESEASOSELE

The melting point range of a eubceances is the narrow batithof femibertenres

between the temperature at which melting begins and the temperature at
which the entire solid has liquefied.

The melting point range of an impure substance is lower and wider than
that of a pure sample of the same substance.
Using an aluminium block

Procedure Thermometer

1 Place a few crystals of the substance

to be melted on the surface of a clean
aluminium block into which a
thermometer has been placed. Rereoioacienistals
2 Use a Bunsen burner or hot plate to
heat the block slowly.
3 Record the melting point range, i.e. ajyminium block
the temperature at which melting
begins and the temperature at which
it ends.
Bunsen burner

Fig. 6.18

Example 6.9
2.4 g of impure benzoic acid was recrystallised and, after drying, 2.1 g of the
purified acid was obtained. What was the percentage yield of purified benzoic
acid?

Answer
Percentage yield ="2.1 x 100% /2.4= 87.5%

Specified Demonstration: Testing solubility of

ionic and covalent substances in different
solvents
In general, ionic or polar covalent substances dissolve in polar solvents such as
water. Non-polar substances dissolve in non-polar solvents such as cyclohexane.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Procedure Rees
1 Measure 3 cm? of water into each of a number of test tubes.
2 Place a spatula tipfull of one of the solid substances into one of the test tubes.
3 Stopper and shake. Note whether the substance has dissolved or not.
4 Repeat this procedure for the other solid substances.
5 Repeat this procedure for all of the solid substances using cyclohexane
as a solvent.
6 Repeat this procedure for the liquids being tested using water and
cyclohexane, respectively, as solvents.
7 Record your results, indicating whether the solute and solvent are polar
or non-polar in each case.

Electronegativity
The ability of an atom in a covalent bond to attract the shared electrons to
itself is given by the atom’s electronegativity value.

Electronegativity is the relative attraction of an atom for

shared pairs of electrons in a covalent bond.

On the Pauling scale of electronegativity, which runs from 0 to 4, the

higher the electronegativity value an atom has, the better it is at attracting
the shared electrons towards itself. As can be seen in the table (Fig. 6.19),
electronegativities increase from left to right across a period, and decrease
from the top to the bottom of a group.

1 Down a group
On going down a group, adding an extra level of electrons shields the outer
electrons from the nucleus, so that even though the nuclear. charge is
increasing, the electrons are not attracted as strongly. This, along with an
increase in atomic radius, results in a decrease in electronegativity.

2 Across a period
Electronegativity increases across a period as the atomic number — the
number of protons in the nucleus — increases and atomic radius decreases.
The larger the nuclear charge and the smaller the atomic radius, the greater
the attraction for the electron pair in a covalent bond.

Predicting the nature of bonds

Electronegativity differences can be used to predict the we oF ond
between two atoms.
1 Ifthe electronegativity difference is zero, the bond can be regarded as being
non-polar covalent. For example, the H—H bond in the hydrogen molecule
(H_,,) and the C-S bond in carbon disulfide (CS,) are both non-polar.
 ||
IONIC AND COVALENT BONDING

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LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

2 In cases where the electronegativity difference is greater than 1.7, the

degree of ionic character is greater than the degree of covalent character,
so the bond is predicted to be ionic. For example, the bond in sodium
chloride (NaCl), where the electronegativity difference is 3.0 — 0.9 =
Ze aS One:
3. The bond is predicted to be polar covalent if the electronegativity
difference is less than 1.7. For example, the bond in hydrogen chloride
(HCl) is predicted to be polar covalent because the electronegativity
difference'is 3:0: —2. 15= 039.

Example 6.10
Use electronegativity values to predict the type of bond in (i) Naf, (ii) CO,,
(iii) PH; and (iv) H,S.
(i) The electronegativity difference between sodium and fluorine is
4.0 — 0.9 = 3.1, which is >1.7. The bonding in NaF is predicted to be ionic.
(ii) The electronegativity difference between carbon and oxygen is
3.5 —2.5 = 1.0, which is <1.7 but >0. The bonding in CO, is predicted to
be polar covalent.
(ili) The electronegativity difference between phosphorus and hydrogen is 2.1
— 2.1 = 0. The bonding in PH, is predicted to be non-polar covalent.
(iv) The electronegativity difference between hydrogen and sulfur is 2.5 — 2.1
= 0.4, which is <1.7 but not much greater than 0. The bonding in H,S is
predicted to be weakly polar covalent.

The valency of an element is the number of bonds each atom of the

element forms when it reacts.
An ionic bond is the electrostatic force of attraction between oppositely
charged ions.
A covalent bond is formed when two atoms share a pair of electrons.
A sigma bond is a covalent bond between two atoms formed by end-on
overlap of orbitals.
A pi bond is a covalent bond between two atoms formed by sideways
overlap of orbitals.
A polar covalent bond is a covalent bond in which there is unequal sharing
of electrons.
Electronegativity is the relative attraction of an atom for shared pairs of
electrons in a covalent bond.
 CHAPTER 7
Shapes of Molecules and
Intermolecular Forces

@@° Topics Covered in this Chapter

@ Shapes of molecules
@ Electron pair repulsion theory
@ Relationship between symmetry and polarity
© Intramolecular bonding and intermolecular forces

Shapes of molecules
Molecules are formed when atoms are joined together by covalent bonds.
The arrangement in space of the atoms dictates the shape of the molecule.

Diatomic molecules consist of just two atoms,

which can be connected by a straight line, so
the shape is said to be linear: for example,
oxygen (O,), hydrogen (H,) and hydrogen _ Fig. 7.1 Beryllium chloride
chloride (HCl). It’ is possible for molecules mee cules creilinear
with more than two atoms to be linear also,
e.g. beryllium chloride (BeCL,).

If a molecule with three atoms is not linear

like beryllium chloride, each atom must be
out of line with the other two. Such
molecules are angular or V-shaped, e.g.
water (H,O).
Fig. 7.2 Water molecules
are V-shaped
Two possibilities arise in molecules with four
atoms, where one is the central atom to which
the other three are bonded. If the four atoms lie
in the same plane with the three outlying
atoms pointing towards the vertices of an
equilateral triangle, the shape is trigonal
planar, e.g. boron trifluoride (BF,).

a
Fig. 7.3 Boron trifluoride
molecules are trigonal planar
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

If the central atom is above the plane of the other

three, but the arrangement is otherwise similar,
the shape is pyramidal, e.g. ammonia (NH,).

Fig. 7.4 Ammonia molecules

are pyramidal

In molecules with four atoms joined to a central

atom, with the four outlying atoms arranged as
far from each other as possible, they are directed
towards the corners of a regular tetrahedron.
This shape is tetrahedral, e.g. methane (CH,).

Fig. 7.5 Methane molecules

are tetrahedral

Electron pair repulsion theory

Electron pair repulsion theory: The electron pairs in the

valence (outer) shell of the central atom repel each other
and end up as far apart as is geometrically possible.

The beryllium hydride molecule (BeH,) has two hydrogen atoms bonded to
the central beryllium atom. Beryllium has just two electrons in its valence
shell and, with each hydrogen atom contributing its sole electron, there are
two bond pairs of electrons in the valence shell of beryllium. These electron
pairs repel each other so as to get as far apart as possible.

The result is a linear arrangement of electron pairs, so the molecule has a

linear shape.
Pie Besa

The bond angle — ZHBeH -— is 180°.

Fig. 7.6
The electronic structure for the boron trifluoride molecule is: x

(72) Fig. 7.7

There are three bond pairs in the valence shell of boron. The furthest apart
that three electron pairs can be arranged is when they are directed towards
the vertices of an equilateral triangle.

The result is a trigonal arrangement of electron pairs, E

so the molecule has a trigonal planar shape.
120 a ew120
Each bond angle (Z FBF) is 120°. E
ee
120

Fig. 7.8

A methane molecule (CH ,) has four bond pairs: H

HiCsH
H

Fig. 7.9

The mutual repulsion causes them to have a H

tetrahedral arrangement. Thus, the methane
molecule has a tetrahedral shape. 109-5
E S

Each bond angle (7 HCH) is 109.5°. bay TT

H
Fig. 7.10

In all molecules containing two, three or four bonding pairs only, the
arrangement of the electron pairs can be predicted or explained by counting
the number of these pairs.

Table 7.1

SB rae 180° Linear BeH, |

| Trigonal planar 1202 Trigonal planar BF, 2
4 Tetrahedral 10o°S? Tetranedral = CH, ~

Lone pairs

:03H HiN3H

oS
Fig. 7.11 Water Fig. 7.12 Ammonia
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Ammonia has one non-bonding electron pair, and water has two. Non-
bonding electron pairs are commonly referred to as lone pairs. The order of
strength of repulsions between electron pairs is as follows:

lone pair: lone pair > lone pair : bond pair > bond pair: bond pair
In ammonia (NH,), the valence shell of nitrogen contains four electron pairs —
three bond pairs and one lone pair. The presence of four electron
pairs indicates a tetrahedral arrangement. However, the presence of
the lone pair causes the bond angle to be about 107° rather than the
expected 109.5°.

Since a lone pair rather than an atom occupies one 107

of the corners of the tetrahedron, the shape of the —N
molecule is pyramidal. H ee |SS H

: H
Fig. 7.13

In the water molecule, there are two bond pairs and

two lone pairsin the valence shell of the central 50
oxygen atom. The distortion is thus greater than in EA a
the case of ammonia, so the expected tetrahedral }y 4945 H
. Nee

angle in the arrangement of electron pairs is

Fig. 7.14
reduced to 104.5°. Since lone pairs rather than
atoms occupy two of the corners of the tetrahedron,
the shape of the molecule is V-shaped.

Table 7.2

NH, 4 a el Distorted 107° Pyramidal —

tetrahedral
HOS AS 2 Distorted ‘104.5° V-shaped
tetrahedral S

Table 7.3 summarises the relationship between the shape of a molecule and
the number and types of electron pairs around the central atom.
 _SHAPES OF MOLECULES AND INTERMOLECULAR FORCES
Table 7.3

2 bonding pairs See ae Linear Se ees BeH,

3 bonding pairs Trigonal planar BF,
4 bonding pairs Tetrahedral CH
3 bonding pairs and 1 lone pair Pyramidal NH
2 bonding pairs and 2 lone pairs — V-shaped HO

Relationship between symmetry and polarity

Coinciding centres ofpositive and negative charge
Sometimes a molerule can be non- Solar overall, even chon) Hie ee
bonds are polar. This occurs when the centre of positive charge coincides
with the centre of negative charge.

Each C—H bond in methane is slightly polar, H™

with the carbon atom having a partial Centre of Centre of
: : positive charge negative charge
negative charge and each hydrogen a partial sensor ye
positive charge. The central carbon atom is ere 7
. . . > Deas

: : at ES
the centre of negative charge, and since the , / st
H"
molecule has a perfect tetrahedral shape, it is a
also the centre of positive charge. That is, the Fig. 7.15
centre of positive charge coincides with the
centre of negative charge and the molecule is
nofi-polar.

A molecule with polar bonds is non-polar when the centres

of positive and negative charge coincide.

Separated centres of positive and negative charge

In the case ofthe'ammonia molecule, which has Contre of
a pyramidal shape, the nitrogen atom at the N negative charge
apex of the pyramid is the centre of negative eal See
charge. The centre of positive charge is at the
H® \ Cente of
geometrical centre of the three hydrogen atoms positive charge
that form an equilateral triangle at the base of
the pyramid. Thus, the centres of positive and Fig. 7.16
negative charge are separated, resulting in a polar molecule.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

A molecule with polar bonds is polar when the centres of

positive and negative charge are separated.

Intramolecular bonding and intermolecular forces

Intramolecular bonding means the bonding within the molecule that
holds the atoms together. An example is the pure covalent bond holding the
two atoms of hydrogen together in a molecule of hydrogen gas.

Intermolecular forces mean forces between molecules. Table 7.4 shows

the types of intermolecular force and the kind of substance in which these
forces are found.

Table 7.4 Intermolecular forces and substances

van der Waals’ forces Non-polar and polar

Hydrogen bonding zy Containing N-H, O-H or H-F bonds
Dipole—dipole interactions Polar

Van der Waals’ forces

Van der Waals’ forces are weak attractive forces caused by the movement of
electrons within a molecule. In the non-polar hydrogen molecule (H,), for
example, the only pair of electrons present is shared equally between the
two hydrogen atoms. Electron movement within the bond may result in
them both being nearer to one atom than the other at a particular point
in time. This creates a temporary polarity — called a temporary dipole — in
the molecule. .
Ho+ a5 Ho-

If two molecules with similar temporary dipoles happen to be orientated

with opposite charges directed at each other, an attractive force will exist
between the two molecules.
Hot aa Ho- BR Sorree 4 Ho+ au Ho-

Another possibility is that a temporary dipole in one molecule will induce a

similar dipole in a neighbouring molecule, with a result similar to the above.
The combined effect of these temporary and induced dipoles is to produce
weak attractive forces — van der Waals’ forces — between neighbouring
molecules, resulting in increased boiling points.
 ___ SHAPESOFMOLECULES
AND INTERMOLECULAR FORCES _
The greater the number of electrons in a molecule, the greater the number
of possible temporary dipoles, and the greater the intermolecular attraction.
This explains why oxygen gas (with 16 electrons per molecule) has a higher
boiling point than hydrogen (with only 2 electrons per molecule).

Dipole- dipole interactions between polar molecules

Dipole—dipole interactions between polar molecules are another example of
intermolecular forces, with similar effects such as higher than expected
boiling points. They differ from van der Waals’ forces in that the dipoles are
permanent due to the polarity in the molecule. Because they are permanent,
they are stronger than van der Waals’ forces.

sf
Cl
Fig. 7.17 Dipole—dipole interactions between hydrogen chloride molecules

Ethene (C,H,,) (M, = 28) and methanal (HCHO) (M, = 30) would be expected
to have similar boiling points due to the similar size of their relative molecular
masses. However, HCHO is polar and the consequent dipole-dipole
attractions cause a much higher boiling point than that of C,H,.

These dipole—dipole attractions must be overcome when liquid methanal boils.

Hydrogen bonding
Hydrogen bonding is a specific type of dipole-dipole interaction. It occurs
when hydrogen is bonded to small highly electronegative atoms: O, N or F.

In water molecules, the O—H bond is highly polar due to the large
electronegativity difference between oxygen and hydrogen. Oxygen carries
a partial negative charge and hydrogen carries a partial positive charge.
Consequently, an oxygen atom will have a strong attraction for hydrogen
atoms on neighbouring molecules, and vice versa.

These strong intermolecular forces cause a much higher than expected

boiling point in water, 373 K. Hydrogen bonding is also the main
intermolecular force that holds molecules of water together in ice crystals.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Hydrogen bonding is also evident in ammonia and in hydrogen fluoride,

but not in hydrogen chloride. It is only atoms which are both small and
electronegative, such as F, O and N, that can form hydrogen bonds. In
larger atoms, such as Cl, the charge is too diffuse or scattered to be effective.
Hydrogen bonds are usually many times weaker than covalent bonds, but
many times stronger than other dipole—dipole attractions.

Table 7.5 Intermolecular forces and substances

Type of substance Intermolecular forces

Non-polar van der Waals’ forces

Containing N-H, O-H or H-F bonds Hydrogen bonding and van der
Waals’ forces
Polar (but not containing N-H, O-H Dipole—-dipole interactions and
or H-F bonds) van der Waals’ forces

Molecules with two bonding pairs around the central atom are linear.
Molecules with three bonding pairs around the central atom are trigonal planar.
Molecules with four bonding pairs around the central atom are tetrahedral.
Molecules with three bonding pairs and one lone pair around the central
atom are pyramidal.
Molecules with two bonding pairs and two lone pairs around the central
atom are V-shaped.
Electron pair repulsion theory: The electron pairs in the valence (outer) shell of
the central atom repel each other and end up as far apart as is geometrically
possible. ?
A molecule with polar bonds is non-polar when the centres of positive and
negative charge coincide. .
A molecule with polar bonds is polar when the centres of positive and
negative charge are separated.
Intermolecular forces and substances: (1) van der Waals’ forces are found
in non-polar and polar substances, (2) hydrogen bonding is found in
substances containing N-H, O-H or H-F bonds, (3) dipole-dipole
interactions are found in polar substances.
Substances and intermolecular forces: (1) non-polar substances contain van
der Waals’ forces, (2) substances containing N-H, O-H or H-F bonds have
hydrogen bonding and van der Waals’ forces, (3) polar substances (but not
those containing N-H, O-H or H-F bonds) have dipole-dipole interactions
and van der Waals’ forces.
 CHAPTER 8
Gas Laws and the Mole

@@® Topics Covered in this Chapter |

Particles in solids, liquids and gases
_ Diffusion
Boyle’ s law
~ Charles's law
Gay-Lussac’s law of combining volumes
Avogadro’s law and Avogadro constant
The mole
Relative molecular mass
Molar mass
Calculations involving the mole
Combined gas law
Kinetic theory of gases
Reasons why gases deviate from ideal gas behaviour
Equation of state for an ideal gas
é

s ticles in solids, liquids and gases

It is now generally accepted that all solids, liquids and gases are composed
of particles, which may be atoms or molecules or ions. These particles are
very small.

The differences between solids, liquids and gases are due to differences in
the arrangement and freedom of movement of their particles. The particles
of a solid constantly vibrate. The particles in a liquid are still close together,
but they can slip by one another easily. Gas particles are relatively far apart
and move very rapidly.

Diffusion
_ Diffusion |is the spontaneous spreading out of a substance, due to
the pong movement of its particles.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Diffusion experiments provide experimental evidence for the existence of

particles.

Specified Demonstration: Diffusion of ammonia

and hydrogen chloride gases
Procedure
if es Hemone ation: ammonia ene aydcoeen AER a arees to
diffuse from opposite ends of the glass tube. When ammonia and hydrogen
chloride come in contact with each other, a white cloud of ammonium
chloride is formed. The cloud forms at first nearer the hydrochloric acid end
because the less dense ammonia gas diffuses more quickly.

Cotton wool Ammonium chloride Cotton wool

soaked with soaked with
hydrochloric acid ; ammonia solution

Fig. 8.1

Specified Demonstration: Diffusion of smoke in air

Procedure
1 Ge a ero. meeol Doan ee | |
2 Observe the movement of the smoke through the surrounding air.

Diffusion in liquids is much slower than diffusion in gases.

Specified Demonstration: Diffusion of ink in water

Procedure
1 are Leva fillareece fans water.
2 Using a pipette, carefully place some blue ink under the water at the
bottom of the beaker.
3 Allow to stand overnight.
4 Using a background of white paper, the blue colour of the ink will be
seen to have spread out.
 GAS LAWS AND THE MOLE [0
Gas laws: Boyle’s [aw and Charles’s law
Gases have a number of laws in common governing their physical properties.

Boyle’s law oe
In 1662, the Irish physicist Robert Boyle discovered the war ia eign the |
volume of air varied with changing pressure. He found that at a constant
- temperature

P x V = constant

where P = pressure of the air, and V = volume of the air.

Boyle’s law
At a constant temperature, the volume of a given mass of any gas
is inversely proportional to the pressure of the gas.

discovered that equal volumes of different gases at

constant pressure all expanded by the same amount
for a given rise in temperature.

Jacques Charles

Charles’s law
At a constant pressure, the volume of a given mass of any gas is
directly proportional to the Kelvin temperature.

In mathematical form:

ss V /T = constant

where V = volume of the gas, and T = Kelvin temperature of the air.

LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Gas laws: the laws of Gay-bussac and Avogadro

Gay- bussac’ slaw of combining volumes
EHOT AHAB OTHEHOSOHEHESEOHOHEOHOHESHHAHEEHRTHEOHSOSEHEDSE eseoneoe ese
COOH

By 1808, the French chemist Joseph Gay-Lussac was able to state his law
of combining volumes.

Joseph Gay-Lussac

Gay-Lussac’s law of combining volumes

When gases react, the volumes consumed in the reaction bear a
simple whole number ratio to each other, and to the volumes of any
gaseous product of the reaction, if all volumes are measured under
the same conditions of temperature and pressure.

Avogadro’ $ law
SHSAHARHEHRHHOGOHRGSOHHSSIKHSHARHAHSSHHSHHRETESHSHSHSHSSHESHHSHSHSTHSSCSHEHRESSHHEKHOHESHO
CES HSETEHSESEEESS

In 1811, che Italian chemist Amedeo veeaee stated what is now known
as Avogadro’s law.

Amedeo Avogadro

Avogadro's law
Equal volumes of gases, under the same conditions of temperature
and pressure, contain equal numbers of molecules.
 GAS LAWS AND THE MOLE

The mole
The mole is the SI unit of amount of substance.

A mole of any substance is defined as the amount of substance

that contains as many particles (atoms or molecules or ions) as
there are atoms of '*C in 12g of '2C.

The number of atoms of the !*C isotope in 12 g of !*C can be measured.

It is found to be approximately 6x 107°. This is the number of
particles per mole for all substances, and is called the Avogadro
constant (L):

L=6x 1073 mol"

Example 8.1
How many atoms are there in 3 moles of helium gas? (Helium gas is composed
of helium atoms.)

Answer
1 mole =6~x 1023 atoms
3 moles = 3 x 6x 1023 atoms
= 18 x 1073 atoms
='1.8 x-107* atoms

Example 8.2
How many molecules are there in 0.1 moles of nitrogen gas? (Nitrogen gas is
composed of molecules.)

Answer
1 mole =6.x 1023 molecules
0.1 moles = 0.1 x 6 x 1023 molecules
= 0.6x 1023 molecules
= 6x 1074 molecules
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 8.3
How many atoms are there in 0.25 moles of carbon dioxide gas? (Carbon
dioxide gas is composed of CO, molecules.)

Answer
1 mole = 6x 1023 molecules
0.25 moles = 0.25 x 6 x 1073 molecules
= 1.5 x 1023 molecules

In every CO, molecule, there are 3 atoms.

Number of atoms in 0.25 moles of carbon dioxide = 3 x 1.5 x 10?
=45~x 1023

Example 8.4
A sample of hydrogen gas contains 1.5 x 1074 molecules. How many moles is
this?

Answer
6 x 1023 molecules =1 mole
1.5 x 1022 molecules = 1.5 x 1072/6 x 1023 moles
= 0.025 moles

Molar volume of gases

One mole of any gas should occupy the same volume as one mole of any
other gas under the same conditions of temperature and pressure. It is
usual for volumes of gases to be compared at a standard temperature and
pressure.

Standard temperature and pressure (STP)

Pressure = 101325 Nm? = 101325 Pa
Temperature = 273 K

The volume occupied by one mole of a gas at STP is called the molar
volume at STP of the gas. It can be taken to be the same for all
gases.

Molar volume at STP = 22.4 | = 22,400 cm? = 2.24 x 10-2m?

 GAS LAWS AND THE MOLE

Example 8.5
What is the volume in litres at STP of 0.05 moles of fluorine gas?

Answer
1 mole = 22.4| at STP
0.05 moles = 0.05 x 22.41 at STP
=a

Example 8.6
How many moles are there in 560 cm? of hydrogen gas at STP?

Answer
22,400 cm? at STP = 1 mole
560 cm? at STP = 560 / 22,400 moles
= 0.025 moles

Relative molecular mass

The relative molecular mass (M,) of a substance is the average

mass of a molecule of the substance relative to one-twelfth of the
mass of an atom of '7C.

Example 8.7
Calculate the relative molecular mass of (i) sulfur dioxide (SO), (ii) nitric acid
(HNO,).

Answer
(i) MSO.) = {S32 492 X 16'= 32.4 32:= 64
(ii) MAHNO3)=1x
1+1x 14+3x 16
=1+14+48
= 63

Molar mass ~*~

The molar mass of a substance is the mass in grams of one mole
of the substance.

The molar mass of a substance has the same numerical value as its relative
3 . 2) 4
molecular mass. Relative molecular mass is measured on the !C scale, while
molar mass is measured in, g mol.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 8.8
What is the mass of 5.5 moles of carbon dioxide?

Answer
M(CO,) = 44
Mass of 1 mole of carbon dioxide =44g
Mass of 5.5 moles of carbon dioxide = 5.5 x 44g
= 242 6

Example 8.9
How many moles in 14 g of nitrogen?

Answer
MAN,) = 28
28g =mass of 1 mole of nitrogen
14g =mass of 14/28 moles
= 0.5 moles

More calculations involving the mole

In solving more complicated problems that involve moles, the following
diagram, showing the relationship between a mole of a substance, its mass,
its volume at STP and the number of its particles, may be useful.

a
x 22.4 Volume of X
Moles of X (if a gas at STP)
in litres at STP

Number of :
particles of X Mass of X ing

Fig. 8.2
 ce ae = ; GAS LAWS AND THE MOLE

Example 8.10
How many molecules are there in 560 cm? of chlorine gas at STP?

Answer
22,400 cm? at STP = 1 mole
560.cm? at STP = = 560 / 22,400 moles
= 0.025 moles
1 mole = 6x 1073 molecules
0.025 moles = 0.025 x 6x 107? molecules
= 0.15 x 1023 molecules
= 1.5x 1024 molecules

Example 8.11
How many atoms are there in 840 cm? of butane gas at STP, given that the
chemical formula for butane is C,H,,?

Answer
22,400 cm? at STP = 1 mole
840 cm? at STP == 840 / 22,400 moles
= 0.0375 moles
1 mole = 6x 1023 molecules
0.0375 moles = 0.0375 x 6 x 1023 molecules
= 0.225 x 1023 molecules
= 14x 0.225 x 1023 atoms (since there are 14 atoms in
each butane molecule)
= 3.15 x 1023 atoms

Example 8.12
What is (i) the volume at STP and (ii) the number of molecules in 24 g of
sulfur dioxide?

Answer
(i) M{SO,) = 64
64 g SO, = 1 mole
24 g SO, = 24/64 moles
= 0.375 moles
1 mole = 22:41 at SIP
0.375 moles = 0.375 x 22.4 |
= 6.4)
(ii) 1 mole = 6x 1023 molecules
0.375 moles = 0.375 x 6x 1023 molecules
= 2.25~x 1023 molecules
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 8.13
What is the mass in g of 140 cm? of oxygen gas at STP?

Answer
22,400 cm? of oxygen gas at STP = 1 mole
140 cm? of oxygen gas at STP, = = 140 / 22,400 moles
= 0.00625 moles
M,(O5) =132
1 mole O, = 32.9
0.00625 moles O, = (0.00625 x 32.9
=

Combined gas law

Boyle’s law, Charles’s law and Avogadro’s law can be grouped together to
give the combined gas law:

PNG era

where P,, V, and T, are the initial pressure, volume and Kelvin tempera-
ture, respectively, and P,, V, and T, are the final pressure, volume and
Kelvin temperature, respectively.

Example 8.14
If a definite mass of gas occupies 500 cm? at a pressure of 101,000 Pa and a
temperature of 27°C, what is its volume in cm? at STP?

Answer

NMA erAr
Tye
P, = 101,000 Pa P, = 101,325 Pa
V, = 500 cm? Wei Suecmiy
T, = 27°C T, =273K
=2/+42/3K
= 300 K

101,000 x 500 ONS 2Z5XV5

300 = 273
Vv — 101,000
x 500 x 273
2 as 300
x 101,325

= -453:5.cm*
 GAS LAWS
ANDTHEMOLE
Kinetic theory of gases
The kinetic theory of gases was developed by
James Clerk Maxwell and Ludwig Boltzmann
towards the end of the nineteenth century. In this
theory, it is assumed that:
1 Gases are made up of particles whose diameters
are negligible compared to the distances
between them.
There are no attractive or repulsive forces ¥

between these particles. James Clerk Maxwell

The particles are in constant rapid random

motion, colliding with each other and with the
walls of the container.
The average kinetic energy of the particles is
proportional to the Kelvin temperature.
All collisions are perfectly elastic (for example,
ifaparticle travelling at 450 ms“! collides with
a wall of its container, it rebounds with the
same speed).

Ludwig Boltzmann

The kinetic theory is only completely valid for ideal gases.

An ideal gas is a gas that obeys all of the assumptions of the

kinetic theory under all conditions of temperature and pressure.

Why gases deviate from ideal gas behaviour

The behaviour of real gases deviates from that of an ideal gas to the greatest
extent at low temperatures and at high pressures. One of the assumptions
of the kinetic theory is that the diameters of gas particles are negligible
compared to the distances between them. At low temperatures and at high
pressures, the diameters are not negligible compared to the distances
between them.

Another assumption of the kinetic theory is that there are no attractive or

repulsive forces between these particles. At low temperatures and at high
pressures, this assumption is not valid, because the gas particles are in close
proximity to each other. The stronger the intermolecular forces, the more
unlike an ideal gas will be a real gas under these conditions.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Real gases behave most like an ideal gas at high temperatures and at low
pressures. Under these conditions, the particles of a real gas are relatively far
away from each other, and the assumptions of the kinetic theory are
reasonably valid.

Example 8.15
State which of the following gases you would expect to come closest to ideal
behaviour, and which you would expect to deviate most from ideal behaviour:
H,, HF, F,. Explain your answers.

Answer
Hydrogen molecules and fluorine molecules are both non-polar, with only van
der Waals’ forces between their molecules. Hydrogen fluoride molecules are
polar, with hydrogen bonding and van der Waals’ forces between their
molecules.

Hydrogen fluoride will deviate most from ideal behaviour because it has the
strongest intermolecular forces. The van der Waals’ forces between hydrogen
molecules are weaker-than those between fluorine molecules because there
are fewer electrons in a hydrogen molecule. Therefore, hydrogen will come
closest to ideal behaviour because it has the weakest intermolecular forces.

Equation of state for an ideal gas

The equation of state for an ideal gas is usually written as follows:

PV = nRT

where P = pressure, V = volume, n = number of moles, R is a constant

known as the universal gas constant, and T = Kelvin temperature.

The value of R is 8.31 J K“'mol"!.

The relationship PV = nRT is referred to as the equation of state for an ideal

gas because it is obeyed only approximately by real. gases.

Calculations involving the ideal gas law

It is important to use units that are consistent with those of the universal
gas constant (R) when doing calculations involving the ideal gas law. The
units of R are J K~'mol-!. The units for V, P, T and n that are consistent
with this are shown in Table 8.1.
 GAS LAWS AND THE MOLE |
Table 8.1

Volume

Pressure Pa

Temperature K

Number of moles mol

Example 8.16
2.5 kg of carbon dioxide gas are released into the air when a fire extinguisher
is discharged. What volume does this gas occupy at a pressure of 100,000 Pa
and a temperature of 288 K?

Answer
PV =rniRT
P = 100,000 Pa
+ Oa
n = 2500/44 moles = 56.82 moles
R =8.313 kK'mol'!
Tr = 288 K
Vo =nRT/P= 56.82 x 8.31 x 288/ 100,000 m? = 1.36 m?

Example 8.17
20 g of a gas occupies a volume of 5 | at 87°C and 200,000 Pa.
(i) How many moles of the gas are present?
(ii) What is the relative molecular mass of the gas?

Answer
() PV=nkRT
P = 200,000 Pa
V =-5|=5~x 10°3 m3

R =8.31)K"'mol'
T =87°C
= 360K 200,000
x5x 1073
n = amount of gas in moles =PV/RT = 531x580

=i0:334

(ii) 0.334 moles of the gas =20g

1 mole has a mass of 20 / 0.334 g = 59.88 g

A volatile liquid is a liquid that is easily vaporised.

LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Mandatory Experiment 8.1: Determination of the

relative molecular mass (M,) of a volatile liquid
Procedure
H Two-thirds fill a beaker with Foil intopthewith a hole
centre

water, and heat to almost boiling

with a Bunsen burner. Control
the flame so that the temperature
remains at about 95°C.
Cut a circle of aluminium foil Propanone
a little more than large enough ee
to cover the mouth of a clean
dry conical flask and fold
down a little around the sides
of the flask.
Find the total mass of the conical
flask, the aluminium foil and a
rubber band. Add 3 to 4 cm? of Fig. 8.3
propanone to the flask.
Cover the mouth of the flask with the aluminium foil. Secure it tightly
with the rubber band so that no vapour can escape. With the pin, prick
one small hole in the centre of the aluminium foil cap. Attach the
clamp to the neck of the flask.
Immerse the conical flask into the boiling water (Fig. 8.3). Holding
the clamp, move the flask up and down periodically to check the
liquid level in the flask.
The volatile liquid will vaporise and some of it will escape out
through the hole in the cap. When the flask appears to be empty (i.e.
all the liquid appears to have evaporated), remove the flask from the
beaker immediately. Record the exact temperature of the hot water,
using the thermometer.
Allow the flask to cool — most of the vapour will condense. Then,
thoroughly dry the outside of the flask, including the foil. Find the
mass of the flask, cap, rubber band and contents> By subtraction, find
the mass of liquid vaporised.
Remove the cap and rubber band. Find the volume of the flask by
completely filling it with water, and then transferring all of the liquid
from it to graduated cylinders.
Observe the value of atmospheric pressure using a barometer, and
record this value.
Calculate the value of the relative molecular mass (M_) of the volatile
liquid.
A sample calculation is shown in Example 8.18.
 __GAS LAWS AND THE MOLE
Example 8.18
In an experiment to measure the relative molecular mass of a volatile liquid,
_the following results were obtained:

Mass of condensed vapour of volatile liquid =O.75:9

Atmospheric pressure = 100,705 Pa
Temperature of boiling water (= temperature of vapour) = 370 K
Volume of flask (= volume of vapour) 229 X10 ne
What is the relative molecular mass of the volatile liquid?

Answer
PV =nRT
=e PVR I,
me = 100,705 x 2.9 x 104 18.31.6370
=>n =0.0095 moles
n =m/M.
=>M,=m/n
=> M. = 0.75 / 0.0095
=>M, = 78.95

Diffusion is the spontaneous spreading out of a substance, due to

the natural movement of its particles.
Boyle’s law: At a constant temperature, the volume of a given mass of any
gas is inversely proportional to the pressure of the gas.
Charles's law: At a constant pressure, the volume of a given mass of any
gas Is directly proportional to the Kelvin temperature.
Gay-Lussac’s law of combining volumes: When gases react, the volumes
consumed in the reaction bear a simple whole number ratio to each other,
and to the volumes of any gaseous product of the reaction, if all volumes
are measured under the same conditions of temperature and pressure.
Avogadro's law: Equal volumes of gases, under the same conditions of
temperature and pressure, contain equal numbers of molecules.
A mole of any substance is defined as the amount of substance that
contains as many particles (atoms or molecules or ions) as there are atoms
GPC in 479 of 12C.
The relative molecular mass (M,) of a substance is the average mass of
a molecule of the substance relative to one-twelfth of the mass of an atom
fe Ge
The molar mass of a substance is the mass in grams of one mole of the substance.
An ideal gas is a gas that obeys all of the assumptions of the kinetic theory
under all conditions of temperature and pressure.
A volatile liquid is a liquid that is easily vaporised.
 CHAPTER 9
Stoichiometry, Formulas
and Equations

eo. Topics Covered inthisChapter

Empirical formulas
Molecular formulas
Percentage composition by mass
Structural formulas
Balancing chemical equations
Calculations based on balanced chemical equations
Calculations involving excess of one reactant
Percentage yields — .
nar

Table 9.1

Hydrogen -H Chlorine.
Nitrogen NN Benne ep
_Oxygen :oF cae
“Fluorine E, te a

formula ofthe following compound: ethane (C,H,)? oo

a= STOICHIOMETRY, FORMULAS AND EQUATIONS
Empirical formulas from analytical data
Example 9.2
A compound on analysis is found to contain 40% carbon, 6.66% hydrogen
and 53.33% oxygen by mass. What is the empirical formula of the compound?

Answer

Element Percentage Percentage/A, — Simplest ratio

Carbon 40 40/12=73.33 |
Hydrogen 6.66 6.66 / 1 = 6.66 2
Oxygen 53:33 93.337)'16 = 3:35 1

Empirical formula = CH,O

See ees Comer

aeoy abi he) ooh tn
Example 9.3
When 0.48 g of magnesium is heated in excess oxygen, 0.8 g of magnesium
oxide is formed. What is the empirical formula of magnesium oxide?

Answer
Mass of magnesium consumed = 0.489
Mass of oxygen consumed = (0.8 -0.48)g=0.32g
Moles of magnesium atoms consumed = 0.48 / 24 = 0.02
Moles of oxygen atoms consumed = 0:32./-16 = 0.02
Ratio of magnesium atoms to oxygen atoms = 0.02:0.02 =1:1
Empirical formula of magnesium oxide = MgO

eine dotumias fro apcommposiiay aba ok.

Example 9.4
11.6. g of an oxide of iron was heated with carbon and 8.4 g of iron was
formed. What is the empirical formula of the oxide?

Answer
Mass of iron in the compound =8.49
Mass of oxygen in the compound =(11.6-8.4)g=3.29
Moles of iron atoms inthe compound =8.4/56 =015

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Moles of oxygen atoms in the compound = 3.2 / 16 202

Ratio of iron atoms to oxygen atoms = Ota 7 O22 =e Sich
Empirical formula of iron oxide = Fe,0,

Molecular formulas
The molecular formula of a compound is the formula that
gives the actual number of atoms of each element present in a
molecule of the compound.

The molecular formula of hydrogen peroxide, for example, is H,O,. This

shows that there are two atoms of hydrogen and two atoms of oxygen in
every molecule of the compound.

To find the molecular formula of a compound, both its empirical formula

and its relative molecular mass must be known.

Example 9.5
The empirical formula of ethyne is CH and its relative molecular mass is 26.
Find the molecular formula of ethyne.

Answer
The formula mass of CH = t2+ Pe 13
The relative molecular mass of ethyne = 26
Number of CH units in an ethyne molecule = 26 / 13 = 2
Molecular formula of ethyne ~ =GH, ~

Example 9.6 2
The relative molecular mass of butanoic acid is found to be 88. On analysis,
it is found to contain 54.54% carbon, 9.09% hydrogen and 36.36% oxygen
by mass. Find the molecular formula of butanoic acid.

Answer

Element Percentage Percentage/A, _—_Simplest ratio

Carbon 54.54 54.54/12 =4.545 : 2 | .
Hydrogen 9.09 9.09/ 1 =9.09 4
Oxygen 36.36 36.367 16=72.27 1

(continued)
_- {eS ips _ STOICHIOMETRY, FORMULAS
AND EQUATIONS

Empirical formula of butanoic acid = C,H,0

Formula mass of C,H,O = 44
Relative molecular mass of butanoic acid = 88
Number of C,H,O units in a butanoic acid molecule = 88 / 44 = 2
Molecular formula of butanoic acid = C,H,O,

Percentage composition by mass

If the empirical formula of a compound is known, the percentage by mass
of each element present can be calculated. It is useful, for example, to be
able to calculate the percentage of nitrogen in a fertiliser, as this is a key
nutrient in the fertiliser.

Example 9.7
What is the percentage of nitrogen in ammonium nitrate (NH,NO,)?

Answer
Moles of nitrogen per mole of ammonium nitrate = 2
Mass of nitrogen per mole of ammonium nitrate = 28
Molar mass of ammonium nitrate = 80g mol!
Percentage of nitrogen in ammonium nitrate = 28 x 100/ 80%
='35%

Structural formulas
The structural formula of a compound shows the
arrangement of the atoms within a molecule of the compound.

Table 9.2

Substance Empirical formula Molecular formula Structural formula

Ethene Chis C,H, H
we qi
H
ims H
Ethyne CH C3H; 9 ie Sel

The structural formula of ethene shows that each carbon atom is joined by
single bonds to two eee atoms and by a double bond to the other
carbon atom.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

In ethyne, each carbon atom is joined by a single bond to a hydrogen atom

and by a triple bond to the other carbon atom.

Example 9.8
The structural formula of butane is

Pet Tre uke gat

+ seusree aiacaite
Tat eto
Find (i) its molecular formula and (ii) its empirical formula.

Answer
(i) The molecular formula is found by counting the atoms of each element
in the structural formula.
Molecular formula of butane = C,H,,
(ii) Empirical formula of butane = CH,

Balancing chemical equations

Remember...
In balancing an equation, formulas cannot be altered in any way,
but can only be multiplied by an appropriate number.

Example 9.9
Butane reacts with oxygen, forming carbon dioxide and water vapour only.
Write a balanced chemical equation for the reaction.

Answer
The unbalanced equation is

CH, ~ 0, > CO, +H,0 ~

To balance the equation, each element is checked in turn to see whether or not
there are equal numbers of atoms of that element on the two sides of the
equation.

Carbon: There are 4 carbon atoms on the left-hand side of the equation, so
CO, must be multiplied by 4:

C,H) + 0, > 4CO, + H,0

(continued)
 STOICHIOMETRY, FORMULAS AND EQUATIONS_
Hydrogen: There are 10 hydrogen atoms on the left-hand side, and only 2 on
the right-hand side. HO must therefore be multiplied by 5:

Gita 05-460, +.5H,0

Oxygen: There are now 2 oxygen atoms on the left-hand side, and 13 on the
right-hand side. O, must therefore be multiplied by 6.5:

C,H,9 + 6.50, > 4CO, + 5H,0

Calculations based on balanced chemical equations

Example 9.10
Ethane burns in air, according to the equation

C5He@q) + 3-50.24) > 2CO3(4) + 3H,0)

lf 4 moles of ethane are reacted fully with oxygen, calculate (i) the number of
moles of carbon dioxide formed, (ii) the number of moles of water vapour
formed, and (iii) the number of moles of oxygen consumed.

Answers
From the equation
CHE ig) + 3.50() > 2005/4) + 3H, 0)
1 mole 3.5moles 2moles 3 moles
Therefore: 4 x (1 mole 3.5 moles 2moles 3 moles)
= 4 moles 14 moles 8 moles 12 moles

(i) 8 moles of carbon dioxide, (ii) 12 moles of water, (iii) 14 moles of oxygen.

Calculation of masses of reactants or products from balanced

chemical equation
Sseoeeoneseseseseosenaeens COROSCESESEERTEHEHOTHEHESEHEHHESHEREHOEHOREHOTHEEOHTHHOEHTAEHOHOHRTEHOEHESEHG

Example 9.11
Magnesium reacts with water vapour to form magnesium oxide and hydrogen,
according to the équation

Mg + H20@ > MIO + Fo)

If 60 g of magnesium is reacted with excess water vapour, calculate the mass
of magnesium oxide produced.
(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Answer
60 g Mg = 60/ 24 moles
Mg = 2.5 moles Mg
From the equation

Mg.) + H,O(4) > MgO.) a H5¢q)

1 mole 1 mole 1 mole 1 mole
Therefore: 2.5 moles 2.5 moles 25 moles 2.5 moles

1 mole MgO =40g MgO

2.5 moles MgO = 2.5 x 40g = 100g

Example 9.12
Hydrogen reacts with chlorine to form hydrogen chloride, according to the
equation

Hoi) + Clog) > 2HCI6)

If 11.2 litres of hydrogen (measured at STP) are used to react with excess
chlorine, what mass of hydrogen chloride is formed?

Answer

11.2 litres H, = 11.2 / 22.4 moles H, = 0.5 moles H,

From the equation.
Ho) + Clog) = 2HC|)
1 mole 1 mole 2 moles
Therefore: 0.5 moles _ 0.5 moles 1 mole

1 mole HCI = 36.5 g HCI v

Calculation of volumes of gaseous reactants or products from

balanced chemical equations =
Example 9.13
Butane burns in air, according to the equation

CAH jo) + 6.5054) = 4ACO5 44) + SHO.)

What volume of oxygen (measured at STP) is needed for complete combustion

of 2.9g of butane?

(continued)
 STOICHIOMETRY, FORMULAS AND EQUATIONS _
Answer

2.99 CyHi9 = 2.9/58 moles C,H,,. = 0.05 moles C,H,,

e a4 1019) + 6.5054) — 4CO 4,4) + 5H,0()
1 mole 6.5 moles 4 moles 5 moles
Therefore: 0.05 x (1 mole 6.5 moles 4 moles 5 moles)
= 0.05 moles 0.325 moles 0.2 moles 0.25 moles

1 mole of oxygen at STP = 22.410,

0.325 moles at STP = O92 5x 22, Ais 28"

Other calculations based on balanced chemical equations

SHSSHRSHEETHHSHETHEETHSSHSESHRETHRGSSOSHHSFTOSSHSSSHEHOEHOSHHERHTHHTHHOREHOHHOHEAHREHRHOHHROESE HEHE

Example 9.14
A solution of sodium pede is reacted with enough nitric acid solution to
neutralise it exactly. The equation for the reaction is
NaOH4q+ HNO5;4q) > NaNO3iaq) + H0q)
On evaporation of the water, 170g of sodium nitrate are obtained. Calculate
(i) The number of moles of nitric acid consumed in the reaction.
(ii) The number of water molecules formed.
(iii) The mass of sodium hydroxide used to make up the solution.

Answer

170 g NaNO, = 170/ 85 moles NaNO, = 2 moles NaNO,

From the equation

NaOH.) + HNO5/,4) > NaNO 3,4) oo HOw
1 mole = 1mole 1 mole 1 mole
Therefore: 2 moles 2 moles 2 moles 2 moles

(i) Number of moles of nitric acid consumed in the reaction = 2

(ii) 1 mole H,O0, = 6 107? molecules of H,O
2 molesH,O = 2x 6x 1073 molecules = 12 x 1023 molecules
= 1.2 x 1024 molecules
(iii) 1 mole NaOH = 40 g NaOH
2 moles NaOH = 2 x 40 g = 80g
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Calculations involving excess of one reactant

It often happens that when a chemical reaction is being carried out, one of the
reactants is present in excess. The substance that is not present in excess is
called the limiting reactant, as the amount of this substance present will
dictate how much of each of the products is formed.

Example 9.15 -
Magnesium reacts with sulfuric acid, according to the equation

My) + H2SO 4¢aq) > M9SOaxaq) + Aa(q)

A 250 cm? aqueous solution containing 9.8 g sulfuric acid is added to 6g
magnesium.
(i) Show that the magnesium is present in excess.
(ii) Calculate the mass of magnesium sulfate formed.
(iii) Calculate the volume of hydrogen (measured at STP) formed.

Answer
(i) Moles of magnesium present initially =6/24 =0.25
Moles of sulfuric acid present initially = 9.8 / 98 = 0.1

MQ, i‘ H)SO0 (aq) hi MgSO 444) e Hoi)

1 mole 1 mole 1 mole 1 mole
0.1 moles 0.1 moles 0.1 moles 0.1 moles

Since the 0.1 moles of sulfuric acid that are present initially will react fully
with 0.1 moles of magnesium, and there are 0.25 moles of magnesium
present initially, it is clear that it is the magnesium that is present in
excess. Sulfuric acid is the limiting reagent.

(il) Mo. + HO... > MGSOjiq) + Hoe -

0.1 moles 0.1 moles 0.1 moles 0.1 moles
Amount of magnesium sulfate formed = 0.1 moles
Mass of magnesium sulfate formed =0.1x 120g=12.0g

(iil) Amount of hydrogen formed = 0.1 moles ~

Volume (at STP) of hydrogen formed = 0.1 x 22.41=2.24|

Percentage yields
Actual yield x 100 ,
Percentage yield = ——@———___
pie! Theoretical yield E
 STOICHIOMETRY, FORMULAS AND EQUATIONS

Example 9.16
In an experiment to prepare ethene (C,H,), 6.9 g of ethanol (C,H,OH) was
heated with aluminium oxide and 0.7 g of ethene was formed. Calculate the
percentage yield of ethene. The equation for the reaction is:

CH,OH\) = Co Haig) + HO,

Answer

6.9g C,H,OH = 6.9 / 46 moles C,H.OH = 0.15 moles

C,H,OH,) =xS C,Hag) + H5 0.
1 mole 1 mole 1 mole
0.15 moles 0.15 moles 0.15 moles

Theoretical yield = 0.15 moles C,H, = 0.15 x 28 g C,H, = 4.2 g

Actual yield = 0.7
Actual yield x 100 |, 0.7 x 100
Percentage yield=
Theoreticalyield © 4.2
= 16.2%

Example 9.17
A sample of ethanal was prepared by reacting 9.2 cm? of ethanol (density
0.8 g cm-?) with an acidified solution containing 11 g of sodium dichromate
(Na,Cr,0,.2H,O). The reaction may be represented by the equation

3C,H.OH@ + Ct O52(aq+ SH"aq)> 3CH3CHOy + 2CrF+eq + 7H20,

After purification, it was found that 1.2 g of ethanal were formed.
(i) Determine the limiting reactant.
(ii) _ Calculate the percentage yield of ethanal.

Answer
(i) Density = mass / volume
Mass = volume x density
9.2 cm? of ethanol = 9.2 x 0.8g ethanol = 7.36 g ethanol
= 7.36 / 46 moles
= 0.16 moles
11g sodium dichromate = 11 / 298 = 0.0369 moles

3C,H,OH\)+ CEO + SH yo? 3CH3CHOy) + 20 ince: 7H,0,)

3 moles 1 mole 3 moles 2 moles 7 moles
0.1107 0.0369
(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Since the 0.0369 moles of sodium dichromate that are present will react
fully with 0.1107 moles of ethanol, and there are 0.16 moles of ethanol
present initially, it is clear that it is the ethanol that is present in excess.
Sodium dichromate is the limiting reagent.

(ii) Actual yield = 1.2 g ethanal

3C,HgOH + Cr,0325,) + SHtaq) > 3CH3CHOW + 2Cr%5q) + 7H20%
3 moles 1 mole 3 moles 2 moles 7 moles

Theoretical yield of ethanal = 0.0369 moles x 3. =0.1107 moles

SOAV0LX 44,9 Wa cae OnE G
_ Actualyield x 100, 1.2100 ,
Percentage yield = %
Theoretical yield i ASTI a
= 24.63%

The empirical formula of a compound is the formula that gives the

simplest whole number ratio in which the atoms of the elements in the
compound are present.
The molecular formula of a compound is the formula that gives the
actual number of atoms of each element present in a molecule of the
compound.
The structural formula of a compound shows the arrangement of the
atoms within a molecule of the compound.
Actual yield x 100 ,
Percentage yield = oTrecenclveld

Your revision notes

 CHAPTER 10
Acids and Bases 1

Pee See
Acids, bases and salts
Household acids and bases
Neutralisation reactions
' Arrhenius theory of acids and bases
Brgnsted-Lowry theory of acids and bases
Conjugate acids and bases

Introduction to acids and bases

Acids are substances that turn blue litmus red and usually react with
metals such as zinc, releasing hydrogen. Hydrochloric acid (HCI), sulfuric
acid (H,SO,,) and nitric acid (HN O,) are examples of acids.

Bases are substances that turn red litmus blue and neutralise acids. Sodium
hydroxide (NaOH), sodium carbonate (Na,CO,) and ammonia (NH,) are
examples of bases.

A base that dissolves in water is called an alkali. Sodium hydroxide is an

alkali; a solution of sodium hydroxide is said to be alkaline.

Bases
neutralise acids

| water-soluble |
bs ASCs es

Fig. 10.1

Acids can be classified as monobasic, dibasic or tribasic, depending on the

number of hydrogen atoms per molecule that are removable when reacting
with a base. For example, hydrochloric acid (HCl) is a monobasic acid,
while sulfuric acid (H,SO;,) is dibasic.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Household acids and bases

There are many Eales of household acids. These raclndes ine
which contains the weak acid ethanoic acid (CH, COOH); lemon juice,
containing the weak acid citric acid; and dilute ie acid in car batteries.

Household bases include ammonia (used for cleaning), sodium hydroxide

(used in oven cleaners), and magnesium hydroxide (used as a laxative and
antacid in Milk of Magnesia).

Neutralisation reactions
When an acid reacts with a base, a salt is formed. For example, when
hydrochloric acid reacts with sodium hydroxide,
HCl + NaOH > NaCl + H,O
the salt sodium chloride is formed.

A neutralisation reaction is one in which an acid and a base react

to forma salt and water.

Neutralisation of an acid by a base has many everyday applications. For

example, magnesium hydroxide and sodium hydrogencarbonate are bases
used in stomach powders to treat acid indigestion. The excess hydrochloric
acid is neutralised:

2HC]I + Mg(OH), > MgCl, + 2H,O

Glee NaHCO; > NaCl + 0 GO,

Lime (calcium hydroxide) is a base used in agriculture to neutralise acidic soil.

Arrhenius theory of acids and bases

In 1887, the Swedish chemist Arrhenius developed a theory of acids-and bases.

Svante Arrhenius

An Arrhenius acid is a substance that dissociates in water to form

hydrogen ions.
 ACIDS AND BASES 1

An Arrhenius base is a substance that dissociates in water to form

hydroxide ions.

Arrhenius stated that:

1 An acid is a neutral molecule (HX) which dissociates in water to form
a hydrogen ion and an anion:
HX — Ht + X
2 The acidic properties of the solution are due to the presence of H* ions.
3 A base (MOH) dissociates in water to form a hydroxide ion and a
cation:

MOH — OH” + Mt
4 The basic properties of the solution are due to the presence of OH™ ions.
5) In solution, strong acids and bases are fully dissociated.
6 In solution, weak acids and bases are only slightly dissociated.

According to the Arrhenius theory, neutralisation of a strong acid solution

like HCI by a strong base solution like NaOH occurs as follows:

In solution, the strong acid HCl is fully dissociated into H* and CI ions,
while the strong base NaOH is fully dissociated into Na* and OH™ ions.
When the two solutions are mixed, the H* ions react with the OH™ ions:

H+ + OH- — H,O
The two other ions present, Na® and Cl, do not react.

The Arrhenius theory explains why strong acids only conduct electricity
when dissolved in water; there are no ions present in a pure acid.

The Arrhenius theory also explains why a weak acid solution does not
conduct electricity as well as a strong acid solution of a similar
concentration; there are fewer ions present in the weak acid solution. For
similar reasons, a weak base solution does not conduct electricity as well as
a strong base solution of a similar concentration.

Gronsted-lowry theory of acids and bases

In 1923, Bronsted and Lowry proposed a new and broader theory of acids
and bases, called the Br@nsted-Lowry theory. According to this theory:
1 An acid is a proton donor.
2 A base is a proton acceptor.
3 An acid—base reaction involves transfer of a proton (H*) from the acid
to the base.
4 The stronger the acid, the more readily it transfers a proton.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

5 The stronger the base, the more readily it

accepts a proton.
6 The weaker the acid, the less readily it transfers
a proton.
7 The weaker the base, the less readily it accepts
a proton.

Thomas Lowry

Acid—base reactions, according to the Brgénsted-Lowry theory, involve

proton transfer. When HCl is added to water, the acid (HCl) transfers a
proton to water, which in this case, being a proton acceptor, is a base:

HCl.) ar HOw = H3O0*(aq) ag Clea)

Hydrogen Oxonium
chloride ion

The Brénsted-Lowry theory of acids and bases has a number of advantages

compared to the Arrhenius theory. The Arrhenius theory only deals with
reactions in water. The Brgnsted-Lowry theory broadens the range of
reactions that can be regarded as acid—base reactions. For example,
ammonia reacts with hydrogen chloride gas in the absence of water:

NH) ze HCl) = NHa*(q) + Giza = NH.,Cl,

Ammonia acts as a Brgnsted-Lowry base, because it-accepts a proton from

the Brénsted-Lowry acid, hydrogen chloride.

Remember...
The symbol = indicates that the reactions are
reversible.

The Brgnsted-Lowry theory also explains how substances can be

amphoteric. For example, when water reacts with ammonia it acts as an
acid, donating a proton to ammonia.
 __ACIDS AND BASES 1

When it reacts with nitric acid it acts as a base, accepting a proton from
nitric acid.

(oN
HNO3xaq) + H20) = H3O0%(aq) + NOS(aq)

A Bronsted-Lowry acid is a proton donor.

Example 10.1
Identify the Bronsted-Lowry acids in the following reaction:

HCO,” + H,O0 — HCO, + OH

Answer
When the reaction goes from left to right, H,O acts as a Bransted-Lowry acid,
as it transfers a proton to HCO.-.

When the reaction goes from right to left, H,CO3 acts as a Bronsted-Lowry
acid, as it transfers a proton to OH.

A Br@nsted-Lowry base is a proton acceptor.

Example 10.2
identify the Bransted-Lowry bases in the following reaction:

HCOOH + H,0 = HCOO- + H,0*

Answer
When the reaction goes from left to right, H,O acts as a Bronsted-Lowry base,
as it accepts a proton from HCOOH.

When the reaction goes from right to left, HCOO~ acts as a Bransted-Lowry
base, as it accepts a proton from H,O°.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Conjugate acids and bases

In the reaction of ammonia with water

NH, } H,O == NH, + OH

ammonia is a base, and accepts a proton to form the ammonium ion

(NH,?).
An acid and base such as these that differ by the presence or absence of a
proton is called a conjugate acid—base pair. In the above reaction, H,O
and OH™ form one conjugate pair, while NH, and NH,” form another.
NH; is called the conjugate acid of NH,, while OH” is the conjugate
base of H,O.

A conjugate acid is formed when a proton (H*) is added to a

Bre@nsted-Lowry base.

Example 10.3 :
What is the conjugate acid of HS~?
Answer
The conjugate acid of HS~ is formed when a proton (Ht) is added to it.
Therefore, the conjugate acid of HS~ is H,S.

A conjugate base is formed when a proton (H*) is removed from a

Bronsted-Lowry acid.

Example 10.4 -
What is the conjugate base of H,SO,?
Answer
The conjugate base of H,SO, is formed when a proton (H*)isremoved from
it. Therefore, the conjugate base of H,SO, is HSO,.

Example 10.5
In the reaction of ammonia with nitric acid:

NH, + HNO, = NH,* + NO,

identify the conjugate acid—base pairs.

(continued)
 ACIDS AND BASES 1
_ Answer
When NH, accepts a proton from HNO,, it forms its conjugate acid NH ie
When HNO, donates a proton to NH,, it forms its conjugate base NO, .

The conjugate acid—base pairs are (i) NH, and NH," and (ii) HNO; and NO,.

Conjugate pair
|
NH, + HNO; = NH, + NO;
B-Lbase B-L acid B-Lacid B-Lbase
es at)
Conjugate pair

Us
Thestronger an acid, the weaker its conjugate base. The stronger a
base, the weaker its conjugate acid.

Key Points
A neutralisation reaction is one in which an acid and a base react to *
form a salt and water. oF
An Arrhenius acid is a substance that dissociates in water to form hydrogen
ions. ;
An Arrhenius base is a substance that dissociates in water to form
hydroxide ions. .
A Br@nsted-Lowry acid is a proton donor.
‘A Br@nsted-Lowry base is a proton acceptor.
A conjugate acid is formed when a proton (H*) is added to a Brensted-
Lowry base.
A conjugate base is formed when a proton (H*) is removed from a
Brensted-Lowry acid.
A conjugate acid-base pair is an acid and a base that differ by the presence
or absence of a proton.
 CHAPTER 11
Acid-Base Trtrations

@@ © Topics Covered in this Chapter

® Concentration of solutions
@ Preparation of standard solutions
® Titrations
@® Acid—base titrations

Concentration of solutions
Solutions contain at least two substances, a solute and a solvent. For
example, salt water is a solution in which salt is the solute and water is the
solvent.

Solutions are described as concentrated, if there is a large amount of solute

per litre of solution, or dilute, if there is not. For accurate work, we need to
know the concentration of the solution.

The most useful way of expressing the concentration of a solution is in

terms of moles per litre of solution (molarity).

If one mole of sodium carbonate is dissolved in water and made up to a

total volume of 1 litre with water, a 1 mol |! solution of sodium
carbonate has been made. This may also be written as a 1 M Na,CO,
solution.

If 20 g (0.5 moles) of sodium hydroxide is dissolvedin water, and more

water is then added to make a total volume of 1 litre, a 0.5 M NaOH
solution has been made.

Concentration can also be expressed in terms of grams of solute per

litre (g 17),
2 ee ACID-BASE TITRATIONS

Example 11.1
What is the concentration in grams per litre of a 0.01 M nitric acid (HNO,)
solution?

Answer
Molar mass of HNO, = 63 g mol!
0.01 M HNO, solution contains 0.01 moles = 0.01 x 63 gin 1 litre
Concentration of nitric acid solution = 0.63 9 [F'

Example 11.2
A solution contains 8 g of sodium hydroxide (NaOH) in 250 cm? of solution.
Calculate the concentration of the solution in moles per litre.

Answer
8 g of NaOH in 250 cm? of solution is equivalent to 8 x 1000 / 250
= 32 gin 1 litre
32 g NaOH = 32 / 40 moles NaOH = 0.8 moles NaOH
Concentration of the solution = 0.8 mol I-! 0.8 M)

Example 11.3
What mass of sodium hydroxide (NaOH) is contained in 250 cm? of 0.02 M
sodium hydroxide solution?

Answer
1,000 cm? of 0.02 M NaOH solution = 0.02 moles
250 cm? of 0.02 M NaOH = 0.02 x 250/ 1,000 moles
= 0.005 moles
Molar mass of NaOH = 40 g mol"!
Mass of NaOH contained in 250 cm? solution = 40 x 0.005 g
2.0

Example 11.4
How many moles of hydrochloric acid (HCI) are contained in 25 cm? of 0.2 M
hydrochloric acid solution?

Answer
1,000 cm? of 0.2 M HCI solution = 0.2 moles
1 cm? of 0.2 M HCI solution = 0.2 / 1,000 moles
25 cm? of 0.2 M HCI solution = 0.2 x 25/ 1,000 moles
= 0.005 moles
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

To solve problems such as those in Example 11.4, there is a formula that

may be useful.

Number of moles = volume in cm? x concentration in

moles per litre /1,000

Example 11.5 )
How many moles of nitric acid (HNO,) are contained in 20 cm? of 0.1 M
nitric acid solution?

Answer
Number of moles = volume in cm? x concentration in moles per litre/1,000
= 20 x G1 1,000
= 0.002

In water analysis, a unit of concentration that is very useful is parts per

million (ppm). This is used for very dilute solutions.

1 part per million = 1 milligram per litre

For example, if the concentration of fluoride ion in a water sample is 2 ppm,

this means that there are 2 mg of fluoride ion in every litre of the water.

Example 11.6
The concentration of dissolved oxygen in a water sample is 0.0002 M. Calculate
the concentration of dissolved oxygen in the water sample in ppm.

Answer
Molar mass of O, = 32 g mol! se
There are 0.0002 moles of dissolved oxygen in 1 litre of the water sample.
Mass of O, in 1 litre = 0.0002 x 32g
= 0.0064 g
= 0.0064 x 1,000 mg
=6.4'mg
Concentration of dissolved oxygen in water sample = 6.4 ppm

Concentration expressed iin terms ofpercentages

Goncentracion can also be expressed in terms of pereene co che elucee ~
weight per volume (w/v), volume per volume (v/v), or weight per weight
(w/w). Expressing concentration in terms of % (v/v) is useful in everyday
life. For example, labels on bottles of wine state the percentage of alcohol in
the wine: 11% means 11% (v/v) alcohol in the wine.
 ee ACID-BASE TITRATIONS
Table 11.1

Concentration unit Example _ Meaning

Percentage weight per 3% (w/v) NaCl 3 g NaCl in 100 cm?
volume (w/v) solution solution
Percentage volume per 3% (v/v) alcohol 3 cm? alcohol in
volume (v/v) solution 100 cm? solution
Percentage weight per 3% (w/w) sugar 3 g sugar in 100 g
weight (w/w) solution solution

Example 11.7

A solution contains 20 g potassium hydroxide in 1 litre of solution. Express the

concentration of the solution in % (w/v).

Answer
The solution contains 20 g KOH in 1 litre.
100 cm? of solution contains 20 x 100 / 1,000 g KOH
=2 6. KOH
Concentration of KOH in solution = 2% (w/v)

Example 11.8
A bottle of vinegar, contains 25 cm? ethanoic acid in 500 cm? of solution.
Express the concentration of ethanoic acid in the solution in % (v/v).

Answer
The.solution contains 25 cm? CH,COOH in 500 cm? of solution.
100 cm? of solution contains 25 x 100 / 500 cm? CH,COOH
= 5.cm?. CH,COOH
Concentration of CH,COOH in solution = 5% (v/v)

Example 11.9
A solution contairts 10 g sodium carbonate in 40 g of solution. Express the
concentration of the solution in % (w/w).

Answer
The solution contains 10 g Na,CO, in 40 g of solution.
100 g of solution contains 10 x 100 / 40 g Na,CO,
= 25 g Na,CO,
Concentration of Na,CO, in solution = 25% (w/w)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 11.10
The label on a bottle of wine indicates that the concentration of alcohol in the
wine is 9% (v/v). What volume of alcohol is there in 250 cm? of the wine?

Answer
100 cm? of the wine contains 9 cm? alcohol.
250 cm? of the wine contains 9 x 250 / 100 cm? alcohol.
= 22.5 cm? alcohol

Preparation of standard solutions

A standard solution is a solution whose concentration
is accurately known.

Highly pure substances, called primary standards, are needed to make

standard solutions. Substances such as anhydrous sodium carbonate are
suitable for this purpose. Pure water (deionised or distilled) is used as a
solvent.

A primary standard is a substance that is available in a pure,

stable and water-soluble form, so that it can used to make up
a solution of accurately known concentration.

Mandatory Experiment 11.1: Preparation of a

standard (0.1 M) solution of sodium carbonate
Procedure :
1 Using a balance, measure accurately 202568
o
pure anhydrous
sodium carbonate on a clock glass, and transfer it to a clean 250 cm?
beaker.
2 Add, with stirring, about 50 cm? of deionised water to the beaker.
3 To ensure that all the sodium carbonate has been transferred from
the clock glass, use a wash bottle to rinse the clock glass with deionised
water, and add the rinsings to the beaker.
4 Continue stirring the mixture with a stirring rod until the
sodium carbonate has fully dissolved.
5 Wash off the solution on the stirring rod with deionised water
into the beaker, using a wash bottle.
 ee wt tS en) ACID-BASE TITRATIONS

6 Pour the solution through a clean |

funnel into the 250 cm? volumetric
flask.
7 Using a wash bottle, rinse out the ~~ Graduation
mar
beaker several times with deionised
water, and add the rinsings through
Volumetric flask
the funnel to the solution in the flask.
8 Rinse the funnel with deionised gp ile tes
water, allowing the water to run into
the flask. Fig. 11.1
9 Fill the flask to within about 1 cm of the calibration mark. Then add
the water dropwise, using a dropping pipette, until the bottom of the
meniscus just rests on the calibration mark.
10 Stopper the flask and invert it several times to ensure an evenly mixed
solution.

Effect ofdifution on concentration

If a SESS is coloured, for example. a solerions ae reese
manganate(VII), then the colour intensity depends on the concentration.
Diluting the solution results in a lightening of the colour of the solution.

Calculation ofconcentrations ofdiluted solutions ee

Example 11.11
lf 20 cm? of a 3 M hydrochloric acid solution is diluted to a volume of 1 | with
water, what is the concentration of the diluted acid?

Answer
1,000 cm? of 3 M HCI solution contains 3 moles of HCI.
20 cm? of 3 M HCI solution contains 3 x 20 / 1,000 moles of HCl.
= 0.06 moles of HCI
1 litre of the diluted acid contains 0.06 moles.
Concentration of the diluted acid = 0.06 mol F'= 0.06 M

To solve problems such as that in Example 11.11, there is a formula that

may be useful.

Vai a Mair =
= conc x* M conc
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 11.12
lf 12 cm? of a 0.1 M sodium hydroxide solution is diluted to a volume of
500 cm? with water, what is the concentration of the diluted solution?

Answer

Vain * Magi = Veone * Meone

500 x My,= 12 x 0.1
Mii =12x0.1/500 moll! =0.0024 mol F-*
Concentration of the diluted solution = 0.0024 mol I"!

Example 11.13
What volume of a 2 M sodium hydroxide solution is needed to make up
100 cm? of a 0.1 M sodium hydroxide solution?

Answer
Vail eS Mogi a Ne a Lage
(00201 = 2
V conc = 100x 0.1/2 mol |"! =5cm3
Volume of 2. M NaOH solution needed = 5 cm?

Titrations
The concentration of a solution may be found
experimentally by titrating it with a standard
solution. In a titration, a measured volume of one Burette
solution*is added from a burette to a definite
known volume of the other solution in a conical
flask, until the reaction just reaches completion.

The end-point is often detected using an

indicator. The indicator changes colour at the
end-point. The conical flask is sometimes placed
on a white tile during the titration so this colour
change can be seen more easily.

The instrument used to place a known volume of ype ee

solution in the conical flask is a pipette. This
instrument is designed to deliver a specific
volume of liquid. When filled to the mark ‘it
Fig. 11.2 A burette and
contains slightly more than this volume;
a conical flask in use
however, some of this liquid is retained after
during a titration
(8) delivery. To ensure that the pipette delivers only
118
 ACID-BASE TITRATIONS

the correct amount of liquid, it is allowed to release its contents freely,

and then the tip of the pipette is touched to the inside of the conical
flask for about three seconds.

——- Gg
Fig. 11.3 A pipette

Pipettes and burettes, rather than graduated cylinders, are used to measure
volume in titration experiments because they are more accurate. A number
of other precautions are taken to ensure that titration results are as accurate
as possible:
@ The burette is washed out with pure water and then with the solution
that it is to contain. The solution is then added to it, using a beaker and
filter funnel.
@ The tap of the burette is opened briefly to fill the part of the burette
below the tap.
@ The burette is then filled up, until the level of the liquid is above the
0 cm? mark. The funnel is then removed. The tap of the burette is opened
again to allow the level of liquid to fall to a definite mark. The tap is closed
and the level is then noted. All burette readings are taken with the surface
of the liquid at eye level; the bottom level of the meniscus is then read.
@ The second solution is added to the conical flask using a pipette.
@ Prior to this, the pipette is washed out with pure water and then with
the solution; the conical flask is washed out with pure water only.
@ The conical flask is swirled well after each addition of solution from the
burette. Any solution adhering to the sides may be washed down with
pure water, using a wash bottle.
@ A rough titration is carried out first to determine the approximate end-
point. The titration is then repeated more accurately, with very careful
addition of the solution from the burette as the approximate end-point
is approached. Two consistent titration results (titres) are got in this
way, agreeing within +0.1 cm*. The mean of the accurate titres is taken
as the final result.

Acid-base titrations
Standard solutions of the common laboratory acids cannot usually be
prepared directly, as these acids are not readily available in a sufficiently
pure state. Concentrated hydrochloric acid is volatile — hydrogen chloride
gas starts to escape once a bottle of the concentrated acid is opened.

Concentrated nitric acid is volatile and is likely to decompose.

Concentrated sulfuric acid is hygroscopic, i.e. it readily absorbs water
vapour from the air.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

A solution of the acid can be titrated with a standard solution of sodium

carbonate. The object of this is to standardise the acid, that is, to find its
concentration accurately. The mean titration result is used to calculate the
concentration of the acid solution.

In straightforward titration calculations, where only the unknown

concentration is required, the following formula can be used:
V,x M,x n,=V,x M, x n,

where
V, = volume in cm? of the acid solution used in the titration
M, = concentration of the acid solution
n, = number of moles of the base in the balanced equation for the reaction
V., = volume in cm? of the basic solution used in the titration
M, = concentration of the basic solution
m7 = number of moles of the acid in the balanced equation for the reaction

Example 11.14
In a titration, 25 cm? of a 0.05 M sodium carbonate’solution required 22 cm?
of a hydrochloric acid solution for complete neutralisation. Calculate the
concentration of the hydrochloric acid solution. The equation for the reaction is

2HCliaq) i Na,CO3/.4) => 2NaCl,.4) + H,0w) + CO3(4)

Answer
V,x M, x n,=V,x M, x n,

V, = volume in cm? of the acid solution used in the titration = 22 cm?

M,, = concentration of the acid solution a
n, = number of moles of the base in the balanced equation =1 «
V, = volume in cm? of the basic solution used in the titration = 25 cm?
M, = concentration of the basic solution =0,05M
n, =number of moles of the acid in the balanced equation = 2

22x M, x 1 =25 x 0.05 x 2 i

M, =25 = 0.05 k 2/221)
= 0.114 mol |"!
Concentration of HCI solution = 0.114 mol |"!

The formula V, x M, x n, = V, x M, x n, may also be used to find the

volume of one of the solutions in a titration, provided that the volume of
the other solution and the concentrations of both solutions are known.
 ___ACID=BASE TITRATIONS _
_ Example 11.15
In a titration, what volume of a 0.05 M hydrochloric acid is required to
neutralise 25 cm? of a 0.04 M sodium hydroxide solution? The equation for the
reaction is

HCl (aq) + NaOH (aq) ~ NaCl(a9) + H,0%

Answer
V,xM,xn, =V,x M,xn,
V,x 0.05x 1=25x0.04x 1
V, =25'« 0.04*1/10:05 x 1)
= 20 cm? of HCI

Mandatory Experiment 11.2: Standardisation of

a hydrochloric acid solution using a standard —
solution of sodium carbonate
Methyl orange indicator solution is used. At the end-point — when
neutralisation just occurs — the indicator changes colour from yellow to
peach/pink.

Procedure
1 Rinse the conical flask with deionised water.
2 Rinse the pipette with deionised water and then with sodium
carbonate solution.
3 Using the pipette, place 25 cm? of the sodium carbonate solution in
the conical flask. Add 3 drops of methyl orange indicator.
Pour about 50 cm? of the hydrochloric acid solution into a clean dry beaker.
5 Rinse the burette with deionised water and clamp it vertically in the
retort stand.
6 Using a funnel, rinse the burette with the hydrochloric acid solution.
7 Fill the burette with hydrochloric acid solution above the zero mark.
Remove the funnel. Allow the acid to flow into a beaker until the level
of liquid is at the zero mark.
8 Carry out a rough titration by adding hydrochloric acid solution from
the burette in approximately 1 cm? lots to the conical flask, swirling
the flask constantly, until the colour of the solution in the conical flask
changes. Note the burette reading.
9 Repeat the titration more accurately until two readings agree within
0.1 cm?.
10 Calculate the concentration of the hydrochloric acid solution.
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 11.16
In a titration, 25 cm3 of a sodium hydroxide solution required 19.5 cm? of a 0.1 M
hydrochloric acid solution for complete neutralisation. Calculate the
concentration of the sodium hydroxide solution. The equation for the reaction is

HCl
(aq) + NAOH (aq
(aq) > NaCliagy + A120,

Answer
V,x M,x n, =V,xM,xn,
19.5x 0.1 x 1 =25xM,~x 1
M, = 19.5« 0.1% 1/(25*x 1)
= 0.078 mol I!
Concentration of NaOH solution = 0.078 mol 1!

Mandatory Experiment 11.2(a): A hydrochloric

acid/sodium hydroxide titration and the use of
this titration in making the salt sodium chloride
Procedure
(i) To find the end-point accurately
1 Rinse the conical flask with deionised water.
2 Rinse the burette with deionised water and then with hydrochloric acid
solution.
3 Rinse the pipette with deionised water and then with sodium hydroxide
solution.
4 Using the pipette, place 25 cm? of the unknown sodium hydroxide
solution in the conical flask. Add 3 drops of methyl orange indicator.
5 Fill the burette to the 0 cm? mark with hydrochloric acid solution.
6 Carry out one rough and two accurate titrations. i
7 Calculate the concentration of the sodium hydroxide solution:
(ii) To obtain a sample of salt
1 Place 25 cm? of the sodium hydroxide solution in a beaker, without any
indicator. ;
2 Using your results from part (i) of the experiment, add just enough
hydrochloric acid to exactly neutralise it.
3 Gently heat the solution until all the water has evaporated to dryness.
A sample of sodium chloride will remain in the beaker.

In a calculation involving a standard solution where more than just the

unknown concentration is required, or where a solid is one of the reactants,
an alternative method from first principles should be used. This method can
(122) also be used to solve more straightforward problems.
 ACID-BASE TITRATIONS
Example 11.17
In a titration, 25 cm? of a 0.12 M sodium hydroxide solution required 24 cm?
of a sulfuric acid solution for complete neutralisation. Calculate (i) the number
of moles of sodium hydroxide consumed, (ii) the number of moles of sulfuric
acid consumed, and (iii) the concentration of the sulfuric acid solution. The
equation for the reaction is

HSO4iaq) + 2NAOH (5)> NA,SOjyaq) + 2H30q)

(aq)

Answer
(i) In the titration, 25 cm? of 0.12 M sodium hydroxide solution were used.

1,000 cm? of 0.12 M NaOH solution contains 0.12 moles.

25 cm? of 0.12 M NaOH solution contains 0.12 x 25 / 1,000 moles
= 0.003 moles

(ii) The equation for the reaction is

H>SOg/aqy + 2N@OH4) > Na,SO4/,4) + 24,0)

2 moles of NaOH react with 1 mole of H,SO,.

1 mole of NaOH reacts with 0.5 moles of H,SO,.
0.003 moles of NaOH reacts with 0.003 x 0.5 moles of H,SO,=
0.0015 moles of H,SO,

(iii) In 24 cm? of the H,SO, solution there are 0.0015 moles of H,SO,.
1,000 cm? of H,SO, solution contains 0.0015 x 1,000 / 24 moles
= 0.0625 moles
Concentration of H,SO, solution = 0.0625 mol i.

Example 11.18
What mass of magnesium will react with 20 cm? of a 0.09 M hydrochloric acid
solution? The equation for the reaction is

2HCl 44) + Mg... > MgCl,(aq) +Haig)

Answer
1,000 cm? of 0.0%M HCI solution contains 0.09 moles.
20 cm? of 0.09 M HCI solution contains 0.09 x 20 / 1,000 moles
= 0.0018 moles
From the equation, 1 mole of Mg reacts with 2 moles of HCl.
0.0018 moles of HCI react with 0.0018 / 2 = 0.0009 moles Mg
Molar mass of Mg = 24g mor!
0.0009 moles of Mg = 0.0009 x 24g = 0.0216 g Mg
Mass of Mg =0.0216g
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Applications of acid-base titrations

Example 11.19
A sample of vinegar was diluted from 25 cm? to 250 cm? with water. In a
titration, 25 cm3 of a 0.1 M sodium hydroxide solution required 30 cm? of the
diluted vinegar for complete neutralisation. Calculate the concentration of
ethanoic acid (CH;COOH) in the vinegar in (i) mol IF! and (ii) % (w/v). The
equation for the reaction Is :

CH3COOH(aq)+ NAOH(gq) > CH3COONAga+ HpOp

Answer
(i) The formula V, x M, x n, = V, x M, x n, is used first to find the
concentration of ethanoic acid in the diluted vinegar.

V,xM,xn,=V,x M, xn,
30x M,x Ives 25x 01x17
M, = 25 Grlx.1/(30:x1)
= 0.083 molI!
Concentration of CH,;COOH in diluted vinegar = 0.083 mol I"!
Vinegar was originally diluted from 25 cm? to 250 cm? with water, i.e. a
ten-fold dilution.
Concentration of CH,COOH in vinegar = 10 x 0.083 mol F' = 0.83 M
(ii) Molar mass of CH,COOH = 60 g mol!
Concentration of CH;COOH in g I"! in vinegar = 0.83 x 60
= 49.8
Percentage (w/v) of CH,COOH in vinegar = 49.8 x 100 / 1000
= 498%

Mandatory Experiment 11.3: Determination of

the concentration of ethanoic acid in vinegar
Phenolphthalein indicator is used. At the end-point, the indicator changes
colour from pink to colourless.

Procedure
1 Place 25 cm? of 0.1 M sodium hydroxide solution in a conical flask and
add 3 drops of phenolphthalein indicator.
2 Place 25 cm? of vinegar in a 250 cm? volumetric flask and dilute with
water to the calibration mark.
3 Stopper the flask and invert several times to ensure an evenly mixed
solution.
4 Carry out one rough and two accurate titrations.
 ACID-BASE TITRATIONS
5 Calculate the concentration in mol 17! of ethanoic acid in the diluted
vinegar solution.
6 Calculate the concentration in mol I”! of ethanoic acid in the vinegar.
7 Calculate the percentage (w/v) of ethanoic acid in the vinegar.

Example 11.20
2.91 g of a monobasic acid (HX) were dissolved in water and made up to
250 cm? with water. This solution was titrated with 0.108 M sodium hydroxide
solution. 25 cm? of the sodium hydroxide solution required 22.5 cm? of the HX
solution for complete neutralisation. The equation for the reaction is

HX eat NaOH ,,.)=> NaX (aq) + HO,

(i) "Calculate the concentration in (a) g F' and (b) mol F! of the acid.
(ii) Calculate the molar mass of HX.

Answer
(i)
(a) 2.91 gof HXin250cm? =2.91x 4g=11.64gin 1 litre
Therefore: concentration of HX = 11.64 g I"

(b) V, x M, xn, = x Met

22.5x M, x 1 = Popo One rait
M, = 25x 0.108 x 1/(22.5x1)
= O42 molt!
Concentration of HX solution = 0.12 mol I!

(ii)
0.12, moles has a mass of 11.64 g.
1 mole has a mass of 11.64/0.12 g=97g
Molar mass of HX = 97 g mol"!

Example 11.21
Crystals of hydrated sodium carbonate (Na,CO,.xH,O) of mass 3.15 g were
dissolved in water and made up to 250 cm? in a volumetric flask. 25 cm? of
this solution required 15 cm? of a 0.15 M hydrochloric acid solution for
complete neutralisation. The equation for the reaction is

2HCligqy (aq) + NagCO5 (aq) > ZNAClhaq) + Hy Oy + COn4q

Find (i) the concentration of the sodium carbonate solution, (ii) the value of x
in the formula Na,CO,.xH,O, and (ili) the percentage of water of crystallisation
in the hydrated sodium carbonate.

ie
(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Answer
(i)
V,xM,x n, =V,xM,xn,
155015 x1 =25x M,x 2
M, = 15x 0.15x 1/(25~x 2)
= 0.045 mol I"
Concentration of Na,CO3 solution = 0.045 mol I"!
(ii)
Molar mass of Na,CO3.xH,O = 46+ 12+ 48+ 18x
: = 106 + 18x
Concentration of Na,CO, in mol! = 0.045
Concentration of Na,CO, in g I a3, V5 A and 206
Mass of 0.045 moles of Na,CO3.xH,O = 12.6 g
Molar mass of Na,CO.xH 0 | = 12.6/0.045g hee :
= 280 g mol!
106 + 18x el 2 army toe ae
18x » ; ms = 1/4
y : i oh ‘

Remember...
‘| Hydrated sodium carbonate gradually loses water of crystallisation
over a period of time, so it is not unusual to get a value of x that
-is not a whole number.

Molar mass of hydrated codiurl carbonate = 280 g mol!

Percentage of water of crystallisation in the compound = 174 x 100 / 280%
=62.1% "=

Mandatory Experiment 11.4: Determination

of the amount of water of crystallisation in ca
x. = di *

hydrated sodium carbonate

Methyl orange indicator solution is used. At the end-point the indicator
changes colour from yellow to peach/pink.

Procedure
1 Week BCeuntely rabsve ee 5 2 of hydetedl sodium carbonate into a
beaker.
2 Add about 50 cm? of deionised water and stir to dissolve the sample.
3 Using a funnel, transfer all of the solution into a 250 cm> volumetric
 __ACID-BASE TITRATION [FT
flask. Rinse the beaker with deionised water and add the washings cea
to the volumetric flask. Bor
4 Carefully make up the volumetric flask to the mark. Stopper the flask
and invert several times.
5 Titrate the sodium carbonate solution against 0.1 M hydrochloric acid,
using 25 cm? of sodium carbonate solution in the conical flask and
methyl! orange as indicator.
6 Repeat the titrations more accurately until two titrations agree to within
Ollicem?,
7 Calculate the concentration of the sodium carbonate solution.
ee) Find the formula of hydrated sodium carbonate.
9 Find the percentage of water of crystallisation present in hydrated
sodium carbonate.

Concentration is defined as the amount of solute in a specified | fons

amount of solution. It is expressed in moles per litre of solution (molarity).
Concentration can also be expressed in grams of solute per litre (g I).
A standard solution is a solution whose concentration is accurately known.
A primary standard is a substance that is available in a pure, stable and
water-soluble form, so that it can used to make up a solution of accurately
known concentration. |

Your revision notes

 CHAPTER 12

Oxidation Numbers and

Redox Trirations

@©© Topics Covered in this Chapter

Oxidation numbers
Naming of transition metal compounds
Oxidation and reduction in terms of oxidation numbers
Balancing redox equations using oxidation numbers
Manganate(VII)—iron(ID) titrations '
Iodine—thiosulfate titrations

Oxidation numbers
_

The oxidation number of an atom is defined as the charge that an atom

appears to have when the electrons are distributed according to certain rules.

The main rules are as follows:

i! In free elements, each atom has an oxidation number of 0. For example,
in a nitrogen molecule (N,) each nitrogen atom has an oxidation
number of 0.
The sum of the oxidation numbers of all the atoms in a molecule is 0. For
example, in the water molecule (H,O), where hydrogen has an oxidation
number of +1 and oxygen has an oxidation number of —2, the*oxidation
numbers add up to 0:

H,O
2+1)—2=0
The oxidation number of a simple ion containing-one atom is equal
to the charge on the ion. For example, in a eMac ion (CI) the
oxidation number of chlorine is —1.
The sum of the oxidation numbers of all the atoms in a complex ion is
equal to the charge on the ion. For example, in a nitrate ion (NO);
where nitrogen has an oxidation number of +5 and oxygen has an
oxidation number of —2, the oxidation numbers add up to —1:
NOz
to) tt Ge) eal
 ___ OXIDATION NUMBERS
AND REDOX TITRATIONS [J
5 Hydrogen has an oxidation number of +1 in its compounds, except in
metallic hydrides where it is —1.
6 Oxygen has an oxidation number of —2 in its compounds, except in
hydrogen peroxide where it is —1, and when bonded to fluorine it
ise.
7 The oxidation number of Group 1 elements in their compounds is
always +1, and the oxidation number of Group 2 elements in their
compounds is always +2.
8 The oxidation number of a halogen when bonded to a less
electronegative atom is —1. Fluorine is the most electronegative element
and always has an oxidation number of —1 in its compounds. Chlorine
has an oxidation number of —1 in compounds where it is not bonded to
oxygen or fluorine.

Oxidation states
eesceeoseecee : PHROSROCLETHREEHROEHOKEOHAEEEEE

Oxidation nhenbers Beste aie Sie state of an eens 2

indicated in rule 7, Group 1 and 2 elements in their compounds have just
one normal oxidation state each (1 and 2, respectively). With the
exception of fluorine, the halogens in their compounds have several
oxidation states.

Remember...
All elements have an oxidation state of 0
when uncombined.

The: transition metals each have a number of different oxidation states in

their compounds.

Table 12.1 Oxidation states for transition metals

Element _—Oxidation states

Chromium 256
Manganese 2; 3, 4, 6; 7
Iron ez arb
Copper 32
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Calculationofoxidation numbers
Example 12.1
What is the oxidation number of the sulfur atom in the H,SO, molecule?

Answer
Let the oxidation number of S = x
The oxidation number of H == +1 (from rule 5)
The oxidation number of O == —2 (from rule 6)
Therefore: 2(+1)+x+4(-2) =0 (from rule 2).
Therefore: x =—-2+8=+6

Naming of transition metal compounds

Oxidation numbers are used when naming compounds of transition metals
systematically. In the case of a compound containing two elements only, the
ending ‘“—ide’ is used as usual, and the oxidation number of the metal is
indicated by a roman number in brackets after the name of that metal. An
example of this: is copper(II) oxide.

If the compound contains a complex ion, for example CuNO,, then the
name ends with the name of the complex ion — copper(I) nitrate in this case.
If the compound contains water of crystallisation, then the number of
molecules of water of crystallisation is indicated at the end of the name, as
shown for CuSO,.5H,O. The systematic name of this compound is
copper(II) sulfate-5-water.

Example 12.2
What is the systematic name of MnCl,? *

Answer
Let the oxidation number of Mn = x
The oxidation number of Cl = —1 (from rule 8)
Therefore: x + 2(—1) = 0 (from rule 2)
Therefore: x =2
The name of the compound is therefore manganese(II) chloride.
 _ OXIDATION NUMBERS AND REDOX TITRATIONS

Example 12.3
What is the formula of iron(|l) sulfate-7-water?

Answer
The iron(II) ion has a charge of +2.
The sulfate ion has a charge of —2.
The formula is FeSO,.7H,O

Oxidation and reduction in terms

of oxidation numbers
In tetms of oxidation numbers, oxidation is an increase in oxidation
number, while reduction is a decrease in oxidation number.

In working out what is oxidised and what is reduced in a reaction, the

oxidation number should be written below the atom to which it applies, as
shown in the following examples:

HO CEO. OH"
+1 =2 +6 —2 —2-+1

When doing redox equations, the oxidation number for only a single
atom of each element should be written directly underneath.

Oxidation is an increase in oxidation number.

Reduction is a decrease in oxidation number.

Example 12.4
What is (i) oxidised, (ii) reduced, (iii) the oxidising agent, and (iv) the reducing
agent in the following redox reaction?

As,O, + 21, + 2H,O > As,O, + 4b + 4H"

Answer
Assign oxidation numbers to all of the atoms in the equation, using the rules:
ASjO, * 2l, + 20,0 > ASO. + 4i° + 4H"
+3 -2 0 +1 -2 +5 —2 = +1

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

(i) The oxidation number of arsenic increases from +3 to +5. Therefore,

arsenic is oxidised.
(ii) The oxidation number of iodine decreases from 0 to -1. Therefore, iodine
is reduced.
(iii) lodine is the oxidising agent because it is reduced itself.
(iv) Arsenic is the reducing agent because it is oxidised itself.

Bleaching is a redox reaction. Many domestic bleaches contain sodium

hypochlorite (NaOCl). This is an example of an oxidising bleach. When it
bleaches by oxidation, it is reduced to sodium chloride:
NaOC! > NaCl
+1 -2 +1 +1 -1

Reducing bleaches include sodium sulfite (Na,SO,), used for example in

the paper industry, and sulfur dioxide (SO,), used in solution where it forms
sulfite ions (SO,*"). When sulfite ions bleach by reduction, they are
converted to sulfate ions:
SO?" => S032,
+4 —2 HO?

Balancing redox equations using oxidation numbers

Example 12.5
Balance the following redox equation

Cr,0,7 + Fe? + Ht — Cr?* + Fe?* + H,O

Answer _
1 Assign oxidation numbers to all the atoms in the equation.
C1074 Fe** +H? > Cr* + Fet+ + H,0 ;
+6 =—2 +2 +) +3 +3 +1 =2 -

2 Identify atoms that are oxidised or reduced, include any subscripts attached
to them, and indicate the extent of the change in oxidation numbers:
Cr5: 2446 — +3), i.e. decrease of 2x 3=6 Reduction
Fe: +2 — +3, |.e. increase of 1 Oxidation
3 Since the total increase in oxidation number must equal the total decrease,
the ratio of chromium to iron must be Cry fe = 126
4 Rewrite the original equation and apply the ratio Cr, : Fe= 1:6
Cr,0,2--+ 6Fe2* + Ht > 2Cr3* + 6Fe* + HO
5 Balance the rest by inspection:
Cr,0,*" + 6Fe** + 14H* — 2Cr3+ + 6Fe*+ + 7H,0
 __OXIDATION NUMBERS AND REDOX TITRATIONS {
Redox titrations with wotaccie manganate(VIl)
Titrations using oxidising and reducing agents are called redox titrations, or
oxidation—reduction titrations. In this type of titration, potassium
manganate(VI1) is a very useful oxidising agent. It has the advantages of (1)
reacting completely and (2) acting as its own indicator, giving a sharp end-
point. It has the disadvantage in solution of not being very stable. As a
result, solutions of potassium manganate(VII) have to be standardised
shortly before use by titration against a standard solution of a substance, such
as ammonium iron(II) sulfate.

Ammonium iron(II) sulfate is a primary standard. It is stable and available

in a high state of purity. In acidic conditions, it reacts readily with a
solution of potassium manganate(VII) and the reaction goes to completion.
Standard solutions of ammonium iron(IJ) sulfate are stable. Dilute sulfuric
acid is used along with deionised water in making up these solutions, and
this prevents premature oxidation of the solutions by air to iron(IID.

Potassium manganate(VII) contains manganese in the highly coloured

(VII) oxidation state. Manganese in this state is a good oxidising agent
because it is very easily reduced. If acidic conditions are used, it is reduced
to the (II) oxidation state, which is almost colourless.

The end-point of a titration involving the

Mn(VI).4q) > MII)oe)
reaction is therefore easily detectable — no indicator is necessary. Before the
end-point, all added potassium manganate(VII) solution is decolourised by
reaction with iron(II) ions:

MnO, = ear 5Fe 2+ Boe 8H + oes Min 2+ aay 5Fe 3+ (ear 4H,0,)

At the end-point, all of the iron(II) ions have reacted and added potassium
manganate(VII) solution is no longer decolourised.

If acidic conditions are not used in the titration, the reaction will not be
according to the above equation. Instead, manganese is likely to be reduced
to intermediate oxidation states — for example, Mn(IV) which appears as a
brown precipitate — and not directly to the (II) oxidation state. To prevent
this happening, dilute sulfuric acid is used to make sure complete reduction
of the manganese from Mn(VII) to Mn(II) occurs. Unlike hydrochloric acid,
it does not react with potassium manganate(VIJ). Nitric acid cannot be used
to lower the pH in a redox titration, as it is a powerful Oa aiSing agent
itself.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

In redox titrations involving potassium manganate(VII), the

manganate(VII) solution is placed in the burette and the reducing agent
solution and sulfuric acid solution are placed in the conical flask. Because
the dark colour of the manganate(VII) solution makes the meniscus difficult
to see, burette readings are taken from the top of the liquid level.

Manganate(vil)-iron(I1) titrations
Example 12.6
24 cm? of a potassium manganate(VIl) solution required 25 cm? of a 0.0108 M
ammonium iron(ll) sulfate solution for complete reaction. Calculate the
concentration in mol I-' of the potassium manganate(VIl) solution.

Answer

MnO, = eave 5Fe 2 Wee + SH aa) —> Mn pt fan) 5Fe 34 Ga'* 4H,0,)

V,x M,xn,=V,x M, xn,

24x M,x 5 =25 x 0.0108x 1
M, = 25x 0.0108 x 1/(24 x5)
- = 0.00225 mol I"
Concentration of potassium manganate(VIl) solution = 0.00225 mol |-!

Mandatory Experiment 12.1: A potassium

manganate(Vil)-ammonium iron({t)
sulfate titration
No indicator is needed as the manganate(VII) ions are decolourised in the
reaction until the end-point, when a pale pink colour persists.

1 Wash the pipette, burette and conical flask with deionised water.
2 Rinse the burette with the potassium manganate(VII) solution and the
pipette with the iron(]) solution.
3 Place 25 cm? of the iron(II) solution in the conical flask using the
pipette. Add about 10 cm? of dilute sulfuric acid.
4 Using a funnel, fill the burette with potassium manganate(VID solution,
making sure that the part below the tap is filled before adjusting to zero.
Because of the dark colour of the potassium manganate(VII) solution, take
readings from the top of the meniscus.
5 Carry out a rough titration and a number of accurate titrations until two
titres agree to within 0.1 cm?. The end-point of the titration is detected
by the first persisting pale pink colour.
6 Calculate the concentration of the potassium manganate(VII) solution.
 _ OXIDATION NUMBERS AND REDOX TITRATIONS =|

Applications of manganate(sM)-iron( ft)titrations

SHSSHHHTOOHHTAHHOSHSHOTSTAHSEH OSH HEHREHEEHEEHEEHOHESTEOEEHEESHEOEHEHHSH SO HOCH EH OOH DEEEEHEOES

A standard solution of potassium manganate(VII) can be eed to find the

amount of iron in an iron tablet. In this experiment, a known number of
tablets are first dissolved in dilute sulfuric acid. This solution is then
titrated against a standardised potassium manganate(VII) solution. The
reaction is represented by the equation:

MnO,4-(,,) 2 $
(aq) + 5Fe here sha Mn* (9) f SFE + 4H,0,)

Example 12.7
In an experiment to determine the mass of iron in an iron tablet, five iron tablets
of total mass 1.8 g were dissolved in dilute sulfuric acid and the solution made
up to 250 cm? with deionised water. 25 cm? of this solution required 16.5 cm?
of a 0.005 M potassium manganate(VIl) solution for complete reaction. Calculate
(i) the mass of iron in one iron tablet and (ii) the percentage of iron in the tablet.

Answer

MnO, ~ art 5Fe 2 “eet 8H" 24) a Mn 2 tide 5Fe 3 ete 4H,0,)

V,xM,xn, =V,xM,xn,
16.5 x/0:005 x75 =25xM,~x 1
M, = 10.5 0.005% 5 / (25%1)
= 0.0165 mol F'
Concentration of iron(II) solution = 0.0165 mol |"!
Volume of ironill) solution in total = 250 cm?
Moles of iron in this volume = 0.0165 /4= 0.004125
Mass of iron in this volume ='0,004125 x 56= 01.231 9
(i) ,Mass of iron in each tablet =0.231/ 5= 0.0462 q
Mass of each tablet = 16/5 =.0,36'9
(ii) Percentage of iron in each tablet = 0.0462 x 100/0.36%
= 12.0%

Mandatory Experiment 12.2: Determination of

iron((l) in an iron tablet using a standard
solution of potassium manganate(vil)
Procedure Eseneeees
SCARE RSHEEASOSHOSOSAHHHHSHOTOHSHEOHSTSSSOSOHEHESESTDOHEEHHHEDHOHHROSHESHHAHESHSESETTE

1 Find the mass of five iron tablets.

2 Crush the weighed tablets in a mortar and pestle. Transfer all the
ground material to a beaker and stir to dissolve it in about 100 cm? of
dilute sulfuric acid.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

3 Transfer all of this solution (including washings) to a 250 cm?

volumetric flask and make the solution up to the mark with deionised
water. Stopper the flask and invert it several times.
Wash the pipette, burette and conical flask with deionised water.
5 Rinse the burette with the potassium manganate(VIJ) solution and the
pipette with the iron tablets solution.
6 Place 25 cm? of the iron tablets solution in the conical flask using the
pipette. Add about 10 cm? of dilute sulfuric acid.
7 Using a funnel, fill the burette with potassium manganate(VII) solution,
making sure that the part below the tap is filled before adjusting to zero.
Because of the dark colour of the potassium manganate(VII) solution,
take readings from the top of the meniscus.
8 Carry out a rough titration and a number of accurate titrations until
two titres agree to within 0.1 cm®. The end-point of the titration is
detected by the first persisting pale pink colour.
9 Calculate the concentration of iron(ID in the solution of iron tablets.
10 Calculate the mass of iron in an iron tablet.

fodine-thiosulfate titrations
Iodine reacts with sodium thiosulfate according to the equation:
pe yim
b(aq) mm 25,03 (aq) > 2l (aq) a S40¢ (aq)

Iodine is reduced and is therefore the oxidising agent. The thiosulfate ion is
oxidised.

This reaction is useful in volumetric analysis, as the reaction goes to

completion and the end-point can be easily detected. Neither iodine nor
sodium thiosulfate is a primary standard. Iodine is too volatile, while
sodium thiosulfate is not sufficiently pure. However, a standard solution of
iodine can be used to standardise a sodium thiosulfate solution. Also, a
standard solution of sodium thiosulfate can be used.to standardise an iodine
solution.

In an iodine-thiosulfate titration, the iodine solution is placed in the

conical flask. The thiosulfate solution is added from the burette until the
colour of the mixture in the flask changes from brown to pale yellow. A
freshly prepared solution of starch is then added. The starch acts as an
indicator.

When it is added, it forms a blue-black colour with iodine. This colour

disappears at the end-point.
 ____ OXIDATION NUMBERS AND REDOX TITRATIONS — [
Example 12.8
25 cm? of an iodine solution required 24.5 cm? of a 0.01 M sodium thiosulfate
solution for complete reaction. Calculate the concentration in mol |! of the
iodine solution.

Answer

= = 2
lygaqy + 25293° (aq) > 2 faq) + S406 (aq)
V,x M,x n,=V,x M,xn,
25x M,x 2 =245x 0.01 x 1
M, = 205-0104 1/50
= 0.0049 M
Concentration of iodine solution = 0.0049 mol I-'

Mandatory Experiment 12.3:

An iodine-thiosulfate titration
Before each titration, a standard (0.06 M) solution of iodine is generated in
the conical flask by reacting a standard (0.02 M) solution of potassium
iodate, for each titration, with excess potassium iodide. Iodine is liberated
from iodate and iodide according to the equation:
- +
IG.7
3 (aq) + SI (aq) + 6H (aq) Es 3lo(aq) x 3H, 0 (aq)

Excess potassium iodide is used, because potassium iodide acts to keep the
iodine in solution. This is due to the fact that an equilibrium is set up as
follows:
- eer
|b(aq) +3 (aq) < I; (aq)

I, is much more soluble than I, and it is as I, that the iodine is kept in

solution.

Iodine reacts with sodium thiosulfate according to the equation:

oa + 22
lovaq) + 25293°(aqy > 2! (aqaq) + 3496 (aq)

Procedure
1 Wash the pipette, burette and conical flask with deionised water.
2 Rinse the pipette with potassium iodate solution and the burette with
the sodium thiosulfate solution.
3 Place 25 cm? of the potassium iodate solution in the conical flask using
the pipette, and add 20 cm? of dilute sulfuric acid, followed by 10 cm?
of 0.5 M potassium iodide solution.
4 Using a funnel, fill the burette with sodium thiosulfate solution. (137)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

5 Add the sodium thiosulfate solution from the burette to the flask.
6 Add a few drops of the starch indicator solution just prior to the end-
point, when the colour of the solution fades to pale yellow. Upon
addition of the indicator a blue-black colour should appear.
7 The end-point of the titration is detected by a colour change from blue-
black to colourless. Note the burette reading.
8 Carry out a number of accurate titrations, adding the sodium thiosulfate
solution dropwise approaching the end-point, until two titres agree to
within 0.1 cm’.
9 Calculate the concentration of the sodium thiosulfate solution.

Applications of iodine-thiosulfate titrations

Many commercial bleaches are simply solutions of hypochlorite salts, such
as sodium hypochlorite (NaOCl) or calcium hypochlorite (Ca(OC]),).

To determine the amount of hypochlorite in bleach, the bleach is first

diluted. Hypochlorite ion then is reacted with excess iodide ion in the
presence of acid to generate an iodine solution:
= £ 1 it
ClO (aq) + 2l (aq) +24 (aq) anGl (aq) +r leq) fe HO,

The iodine solution produced is titrated against sodium thiosulfate solution

using starch solution as indicator. Iodine reacts with sodium thiosulfate
according to the equation:

lvaq) + 28,03" faq) — 2 (aq)

aq) + S4Oe?
6 (aq)

Example 12.9
25 cm? of bleach was diluted to 250 cm? with deionised water. It was found
that the iodine solution produced by the reaction of 25 cm? of the diluted
bleach with acidified potassium iodide solution required 18.5 cm? of a 0.1 M
sodium thiosulfate solution for complete reaction. Calculate (i) the
concentration in mol F' of the iodine solution, (ii) the concentration of
hypochlorite in the bleach, and (iii) the percentage (w/v) of hypochlorite in the
bleach.

Answer
lovaq) + 28,037%aq) > 21 (aq)+ $406 (aq)

V,x M, x n, = V, x M, x n,
25x M,x 2 =18.5x0.1x 4
M, ==16.55<202) 321950
=.0 0375

(continued)
 ____ OXIDATION NUMBERS
AND REDOX TITRATIONS.
(i) Concentration of iodine solution = 0.037 M
Concentration of hypochlorite in diluted bleach solution = 0.037 M
(ii) Concentration of hypochlorite in undiluted bleach solution = 0.037 x 10 M
=0.37M
= 74.5 x 0.37911
= 27.565 gb!
(iii) Percentage (w/v) of hypochlorite in bleach
= 2/.565 x 100-/ 1000 = 2.76%

Mandatory Experiment 12.4%: Determination of

the percentage (w/v) of hypochlorite in bleach \y
Procedure
1 Using a pipette, add 25 cm? of bleach to a 250 cm? volumetric flask,
and make the solution up to the mark with deionised water. Stopper the
flask and invert it several times.
2 Wash the pipette, burette and conical flask with deionised water.
3 Rinse the pipette with the diluted bleach solution and the burette with
the sodium thiosulfate solution.
4 Place 25 cm? of the diluted bleach solution in the conical flask using the
pipette.
5 Add 10 cm? of dilute sulfuric acid and 1 g potassium iodide to the
conical flask — an iodine solution is formed.
6 Using a funnel, fill the burette with sodium thiosulfate solution,
making sure that the part below the tap is filled before adjusting to
zero.
7 Carry out a rough titration and a number of accurate titrations until two
titres agree to within 0.1 cm’. Each time, add a few drops of the starch
indicator solution just prior to the end-point, when the colour of the
solution fades to pale yellow. The end-point of the titration is detected
by a colour change from blue-black to colourless.
8 Calculate the concentration of the iodine solution.
9 Calculate the concentration of hypochlorite in the bleach solution.
>

The oxidation number of an atom is defined as the charge that an News

atom appears to have when the electrons are distributed according to
certain rules.
Oxidation is an increase in oxidation number.
Reduction is a decrease in oxidation number.
 CHAPTER 13
Fuels and Heats of Reaction 1

@ © © Topics Covered in this Chapter

Sources of hydrocarbons
Aliphatic hydrocarbons
Homologous series
Naming system
Alkanes
Structural isomers
Alkenes s —
Alkynes . *
Aromatic hydrocarbons
~~

Sources ofhydrocarbons
Hydrocarbons are compounds consisting of carbon and
hydrogen only.

Methane (CH,), the main component of natural gas, is a hydrocarbon. The

fossil fuels crude oil, natural gas and coal are sources of hydrocarbons.

Methane can be produced by the anaerobic decomposition of animal waste

and vegetation. It is produced in an uncontrolledway in slurry pits and
refuse dumps.

Methane is also produced in large quantities in the digestive tracts of

animals such as cattle.

Aliphatic hydrocarbons
Hydrocarbons are part of a large branch of chemistry called organic
chemistry. This is the chemistry of carbon compounds, excluding carbon
dioxide, carbon monoxide, carbonates and hydrogencarbonates.
 _ _ FUELS
AND HEATS OF REACTION
1 =|

Hydrocarbons that consist of straight and branched chains of carbon atoms,

or rings of carbon atoms other than those containing a special ring called a
benzene ring, are called aliphatic hydrocarbons.
H nite Ul te H CH; H
| an Leite el
H—C—C—C—C—H H—C—c—C—H
Ke ye he = We oalisee
Int nl Aol ata! H CH; H
Butane 2,2-dimethylpropane

Fig. 13.1 Structural formulas of some aliphatic compounds

Hydrocarbons that contain a benzene ring are called

aromatic hydrocarbons.

Homologous series
A homologous series is a family of compounds with:
@ The same general formula
@ Successive members differing by CH,
@ Similar chemical properties

Example 13.1
Use the general formula C.H,,.,, to work out the molecular formulas of the first
five members of the alkanes.

Answer
Substituting n= 1 into the formula as follows gives the formula of methane, the
first member of the series:

Og REO CH ay42 sr Oa es CH,

Substituting n = 2, 3, 4 and 5 in turn produces the formulas C,H, for ethane,

CH, for propane, C,H,, for butane and C,H,, for pentane.

Naming system
In the IUPAC naming system, each hydrocarbon name consists of two parts,
the root and the suffix. The roots correspond with the number of carbon
atoms in the longest chain present. The first 10 roots are shown in Table 13.1.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Table 13.1

No. of carbons Root —_No. of carbons~

1 Meth- 6 Hex—
2 Eth— 7 Hept—
3 Prop-— 8 Oct—
4 But- 9 Non-
5 Pent— 10 Dec—

The suffix depends on the homologous series to which the compound

belongs. For example, each alkane has the suffix —ane, each alkene has the
suffix —ene, and each alkyne has the suffix —yne.

Example 13.2
Write the names of the following: (i) the alkene with two carbons, (ii) the alkyne
with three carbons, and (iii) the alkane with six carbons in its longest chain.

Answer
(i) Two carbons means that the root is eth-, and alkenes have the suffix
—ene. Thus, the name is ethene.
(ii) Three carbons means that the root is prop—, and alkynes have the suffix
-yne. Thus, the name is propyne.
(iii) Six carbons means that the root is hex—, and alkanes have the suffix
—ane. Thus, the name is hexane.

Alkanes
The alkanes form a homologous series of aliphatic hydrocarbons of general
formula CH 2n+2°

Table 13.2

Name Formula —
carbons
Methane 5 Pentane CsH,>

Z Ethane 6 Hexane CEH,

3 Propane 7 Heptane CHy6

4 Butane 8 Octane CeHi¢

 FUELS AND HEATS OF REACTION 1.
The formula shown in each case is the molecular formula. The structural
formulas of the first four alkanes are shown in Table 13.3.

Table 13.3

Name Molecular formula —_ Structural formula

H
|
Methane GH, H—C—H
|
H
H H
es
Ethane GH H—C— CH
ES eas
H H
H H H
sats ies
Propane C5H, H—C—C—C—H
ae |
H HH
ee = ee |
eee oo
aah oe
Butane

H H HH

Example 13.3
Draw the structural formula of each of pentane, hexane, heptane and octane.

Answer
Maite con, OA ional s PaWOMg Wat yponne y Roce y Went Eevee

ey ee ee
ean HHH HHH Pentane» Octane

Mette Ho An Ba i OAc ROPE y Sole a See 5 eee

yg ee et
hoe en ey Heptane Hexane
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

In the alkanes, each carbon atom forms four separate single bonds to satisfy
the valency of carbon. All of the compounds discussed so far are referred to
as straight chain molecules, given the absence of any branches or rings. In
the alkane molecules, all of the bonds are single bonds.

Molecules that contain only single bonds are said to be saturated.

Structural isomers
Structural isomers are compounds that have the same molecular formula
but different structural formulas, e.g. butane and 2-methylpropane.

He hematin wet Hons tame

ee eee,
any io w [4
Butane Hi Cea

H
2-methylpropane

Fig. 13.2 The structural isomers of butane

When naming alkane molecules, three factors are taken into account:
1 The number of carbons in the longest straight chain in the molecule.
2 The group(s) attached to the longest chain.
3. The positions on the chain where the group(s) are attached.

The structural isomer of butane is named as follows: ‘

1 Since there are three carbons in the longest chain, the molecule is
regarded as a propane derivative.
2 The presence of a methyl group attached to the longest straight chain
means that the compound is called methylpropane.
1S) Since the methyl group is attached to the second carbon in the chain,
the compound is called 2-methylpropane.

Structural isomers are compounds that have the same molecular

formula but different structural formulas.
 FUELS AND HEATS OF REACTION1

Example 13.4
Draw the structural formulas and write the names of the structural isomers of
pentane (C.H,,).

Answer
The use of molecular models will help in working out the required structures.

(i)
a

De
xmI—N—trx=I—n—tZ=
-XI—A—=z

@ Since there are five carbon atoms in the longest chain, the molecule is
called pentane.

(ii)

ule Be

@)
a
oe Gy
ee

@ Since there are four carbons in the longest chain, the molecule is regarded
as a butane derivative.
@ The presence of a methyl group attached to the longest straight chain
means that the compound is called methylbutane.
@ Since the methyl group is attached to the second carbon in the chain, the
compound is called 2-methylbutane.

(ili)

@ Since there are three carbons in the longest chain, the molecule is regarded
as a propane dérivative.
® The presence of two methyl groups attached to the propane chain means
that the compound is called dimethylpropane. The prefix di— is used to
indicate that there are two methyl groups attached to the straight chain.
@ Since the methyl groups are both attached to the second carbon in the
chain, the compound is called 2,2-dimethylpropane.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 13.5
Draw the structural formula of 2,2,4-trimethylpentane.

Answer
(i) The compound is a derivative of pentane, so there are five carbon atoms
in the longest straight chain:
-C-C-C-C-C-
(ii) Trimethy/ indicates that there are three methyl groups (CH,) attached to
the straight chain.
(iii) The numbers 2,2,4— indicate the positions on the chain at which the
methyl groups are attached. Two methyl groups are attached to the
second carbon in the chain, and the third methyl group is attached to
the fourth carbon.

The structural formula of 2,2,4-trimethylpentane is

Ho CHs: He CER IH
Baer
rg eat
He CoO CC eer
gee Bee epee er:
ii Ciba. H

The traditional name of of 2,2,4-trimethylpentane is iso-octane.

Sometimes the structural formula is written in abbreviated or

condensed form.

Example 13.6 %
Draw the structural formula and name the compound CH 3C(CH3),CH >

Answer
The methyl groups in brackets form the branches or side chains. The remaining
three carbons form the longest straight chain, so the compound is a derivative
of propane. The side chain methyl groups are written after the second carbon
in the chain, which means that they are attached to. this carbon. Thus the
compound is 2,2-dimethylpropane. Its structural formula is

Ho Chew
(a
HC
SaiC = Ce
[eee
HCH.
Aa tel: FUELS AND HEATS OF REACTION 1 5

Physical properties of alkanes

The lower members of the alkanes, those up to and including butane, are
gases at normal temperatures. Alkanes from pentane up to alkanes
containing 15 carbon atoms per molecule are liquids; those with more
carbon atoms per molecule than this are waxy solids.

Alkanes are non-polar substances. Because of this, they are insoluble in

water but soluble in non-polar solvents such as cyclohexane and
methylbenzene.

Alkenes
The alkenes form a homologous series of aliphatic hydrocarbons of general
formula C\H, . Each alkene molecule contains a carbon-carbon double
bond, — C = C — , which is the reactive portion or functional group of the
molecule. The lowest member of the series has two carbon atoms.

Alkenes are unsaturated compounds.

Molecules that contain a double or triple bond are unsaturated.

Example 13.7
Use the general formula, C,H,,,, to work out the molecular formulas of the first
two members of the alkenes. Name the compounds and draw their structural
formulas.

Answer
(i) The first member of the alkenes has two carbon atoms. Substituting
n = 2 into the formula as follows gives the required molecular formula:

CoH. => C,H 5,2) = C5H,

All alkenes have a carbon-carbon double bond, so the structural formula is

H en
C=C
eerer east
Ethene

(ii) The second member of the alkenes has three carbon atoms. Substituting
n = 3 into the formula as follows gives the required molecular formula:

CH5, > C3H93) > C3He

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

All alkenes have a carbon-carbon double bond, so the structural formula is

H
Propene

Table 13.4 ;

“No. of carbons Name ——-Molecular formula

oe 7 Ethene e HH,
3 Propene C3He
4 Butene C,H,

Structural isomers of alkenes, which contain four or more carbon atoms, exist.

Example 13.8
Draw the structural formula, write the condensed formula and name the
structural isomers of butene.

Answer
(i)

But-1-ene
ae

In this case the double bond is formed between the first two carbons in
the chain. Since this bond starts at the first carbon in the chain, the
molecule is called but-1-ene. The condensed formula is CH,=CHCH,CH,.
(ii) HHA A
ee ee =
H—C—C=C—C—H
| |
H H
But-2-ene

In this case the double bond is formed between the second and third
carbons in the chain. Since this bond starts at the second carbon in the
chain, the molecule is called but-2-ene. The condensed formula is
CH,CH=CHCH,,.

(continued)
 _FUELS AND HEATS OF REACTION 1

C2
|
H
2-methylpropene

Since the longest straight chain of carbons containing the

carbon-carbon double bond is three, the molecule is regarded as
propene with a branch or side chain. The methyl group is attached to
the second carbon in the chain, so the compound is called
2-methylpropene. The condensed formula is CH,=C(CH3)CH3.

Physical properties of alkenes

The lower members of the alkenes, those up to and including butene,
are gases at normal temperatures. Higher alkenes are liquids or solids.

Alkenes are either non-polar or only slightly polar substances. Because of

this, they have a very low solubility in water but are soluble in non-polar
solvents, such as cyclohexane and methylbenzene.

Alkynes
-The alkynes form a homologous series of aliphatic hydrocarbons of general
formula C_H,,_,. Each alkyne molecule contains a carbon—carbon triple
bond; — C = C -, and this is the functional group of the series. The lowest
member of the series has two carbon atoms.

Alkynes are said to be unsaturated due to the presence of a triple bond.

Example 13.9
Use the general formula, C,H,,,5,to work out the molecular formula of the
first member of the alkynes. Name the compound and draw its structural
formula.

Answer
The first member of the alkynes has two carbon atoms. Substituting n = 2 into
the formula as follows gives the required molecular formula:

CyHon-2 > CoH 29-2 > CoH -2) > C,H,

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

All alkynes have a carbon-carbon triple bond, so the structural formula ts

H—C = C—H
Ethyne

Physical properties ofalkynes

Being compounds of ioe or zero polatiey, heir plese. pope are
essentially the same as those of alkanes and alkenes. The lower members of
the alkynes are gases at normal temperatures, while higher alkynes are
liquids or solids.

Alkynes have a very low solubility in water but are soluble in non-polar
solvents, such as cyclohexane and methylbenzene.

hy
Specified Demonstration: The solubility
properties of methane, ethene and ethyne
Procedure —
1 Threeiaer Allaa testanit fai water.
2 Fit the stopper and delivery tubes to the test tube as illustrated. The
short leg does not reach the surface of the water and the long leg dips
well below the surface.
3 Empty syringe A of any air by pushing the piston in as far as possible.
Connect it to the short-legged delivery tube.
4 Fill syringe B with methane gas as far as the 10 cm? mark. Connect
syringe B to the other delivery tube.
5 Slowly force the methane gas into the water by pushing on the piston of
syringe B.
6 Note the extent, if any, to which the piston in syringe A is pushed back
by gas emerging from the water. Note the degree of solubility of
methane in water.
7 Repeat steps 1-6 using ethene and ethyne gases, with water as the
solvent. \
8 Repeat the experiment for all three gases using cyclohexane and
methylbenzene in turn as solvents.
9 It will be found that methane, ethene and ethyne are insoluble in water
but soluble in cyclohexane and methylbenzene.
 ee ee ee ______ FUELS AND HEATSOF REACTION 1 Ste

Syringe B Syringe A

3 2 a a
ritelfrtedirial

Plastic syringe containing

10cm? of the gas being tested

Fig. 13.3

Chemical reactions of ethyne

Like most hydrocarbons, ethyne gas burns in air to form carbon dioxide and
water vapour.

C54) + 1,0 444) > 2004) + H,0%)

The carbon dioxide may be detected using the limewater test.

Mandatory Experiment 13.1: Preparation

and properties of ethyne
Calcium dicarbide reacts with water, producing ethyne and calcium
hydroxide:
CaCl... + 2H,0w + Nr) + Ca(OH) (9)

Impurities present in the gas, such as hydrogen sulfide and phosphine, can
be removed by bubbling the gas through acidified copper sulfate solution.

The impurities are caused by the hydrolysis of traces of calcium sulfide and
calcium phosphide present in the calcium dicarbide.

Procedure
SOC OHOESESEDEHOEESSHESESTOHOHRSHOEEOEHEHRSSSOTSESHOSH
THEO TSEHTHHESHEOHEHHHEEHHSHOREEHEOESOBSEHOEED

Preparation
1 Place a few pieces of calcium dicarbide (a grey solid) in a Biichner flask
and set up the apparatus as in the diagram.
2 Add water from the dropping funnel, a few drops at a time.
3 Collect the gas produced in test tubes by displacement of water. Stopper
each gas-filled test tube under water. Discard the first test tube filled, as
it contains a mixture of air and ethyne.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Tap funnel

| Water

4 ; \ \ Ethyne
Flask me \

r \

«
, : Acidified
Calcium carbide copper sulfate
solution

Fig. 13.4

Investigation of properties
1 Ignite a test tube of the gas. The flame will be very sooty. Add a few
drops of limewater to the test tube, stopper and shake well. The
limewater turns milky.
2 Add a few drops of a solution of bromine water to a test tube of gas,
stopper quickly and shake well. The red/brown bromine water
decolourises, indicating that ethyne is unsaturated.
3 Add a few drops of acidified potassium manganate solution to a test tube
of gas, stopper quickly and shake well. The purple potassium manganate
solution decolourises, indicating that ethyne is unsaturated.

Uses of ethyne
Ethyne is commonly known as acetylene gas. Due to its high proportion of
carbon, it burns in air with a sooty flame. However, when it is burned while
mixed with pure oxygen it produces a clear flame of about 3000°C. This
makes it suitable for cutting and welding, and it is used for those purposes
in an oxyacetylene torch.

Aromatic hydrocarbons
Aromatic hydrocarbons are compounds that contain a benzene-type ring.
Benzene itself (C.H,) is the most important aromatic compound.

The benzene molecule consists of six carbon atoms joined to form a ring.
There is one hydrogen atom attached to each carbon.
 FUELS AND HEATS OF REACTION 1

In benzene, the carbon-carbon bonds are intermediate between

carbon—carbon single and double bonds. This special type of bonding is
indicated in the structural formula of benzene by a circle drawn inside a
regular hexagon. Each corner of the hexagon represents a carbon atom
bonded to a hydrogen atom.

pie
f
Onn
RSC ee py
H — Sas == FI

|
H

Benzene

In methylbenzene, an organic solvent, the methyl group (CH,) replaces a

hydrogen atom in the benzene molecule. In ethylbenzene, a hydrogen atom
in benzene is replaced by the ethyl group (i):

CH; CH.CH;

Methylbenzene (C7Hs) Ethylbenzene (CeHio)

Physical properties ofaromatic hydrocarbons

The physical properties of the aromatic hydrocarbons are Bari? to those nF
the aliphatic hydrocarbons. Being non-polar, they do not dissolve to any
extent in water, but dissolve in non-polar solvents. Liquid aromatic
hydrocarbons, such as methylbenzene, are themselves good non-polar
solvents, dissolving non-polar solutes readily.

Aromatic hydrocarbons of lower relative molecular mass, such as benzene,

methylbenzene and ethylbenzene, are liquids at room temperature, while
those of higher relative molecular mass are solids.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Specified Demonstration: Solubility properties

of methylbenzene, using cyclohexane, water,
sodium chloride, ethyl! ethanoate, cooking oil
and iodine crystals as solutes
Procedure
Approximately half fill a test tube with methylbenzene.
Add a small quantity of one of the solutes — a few crystals in the case of
the solids, a few drops in the case of the. liquids.
Stopper the test tube and shake vigorously.
Open the test tube carefully in case there is a build-up of pressure.
Decide by inspection whether or not the solute has dissolved.
Repeat in turn for each of the solutes.
It will be observed that only non-polar solutes such as cyclohexane will
have dissolved in methylbenzene.

Hydrocarbons are compounds consisting of carbon and hydrogen

only.
Hydrocarbons that contain a benzene-type ring are called aromatic
hydrocarbons.
A homologous series is a family of compounds with: (1) the same general
formula, (2) successive members differing by CH,, and (3) similar chemical
properties.
Molecules that contain only single bonds are said to be saturated.
Structural isomers are compounds that have the same molecular formula
but different structural formulas. E.
Molecules that contain a double or triple bond are unsaturated. ~

Your revision notes

 CHAPTER 14
Fuels and Heats of Reaction 2

@® © Topics Covered in this Chapter

Exothermic and endothermic reactions
Heat of reaction
Bond energy
Heat of combustion
Heat of formation
Hess’s law
Oil refining and its products
Natural gas
Petrol and the internal combustion engine
Octane numbers
Additives
High-octane compounds
Isomerisation
Dehydrocyclisation
Catalytic cracking
Hydrogen .
Steam reforming
Electrolysis of water

Exothermic and endothermic reactions

Energy is needed to break bonds and is given out when new bonds form.

If the amount of heat produced in forming bonds is greater than the amount
needed to break bonds, heat is given out and the temperature of the reaction
mixture increases. Such a reaction is said to be exothermic. Most chemical
reactions are of this type, e.g. burning fuels.

An exothermic reaction is a reaction that gives out heat to

the surroundings.

If the amount of heat produced in forming bonds is less than the amount
needed to break bonds, heat is taken in from the surroundings and the
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

temperature of the reaction mixture decreases. Such a reaction is said to be

endothermic, e.g. the manufacture of hydrogen by the steam reforming of
natural gas.

An endothermic reaction is a reaction that takes in heat from

the surroundings.

One of the most important properties of hydrocarbons is that they burn in

air or oxygen, producing carbon dioxide and water vapour. Heat 1s
produced in combustion reactions, so they are classified as exothermic
reactions. The large amount of heat produced when alkanes burn makes
them particularly suitable as fuels.

Methane, the first member of the alkanes, is the principal component of

natural gas. Propane and butane are used as bottled gas and are the main
components of LPG (liquid petroleum gas) for use in cars. Petrol is made
up of a large number of different compounds, mostly alkanes.

Specified Demonstration: Demonstration of

(i) an exothermic reaction and
(ii) an endothermic reaction
Procedure
(i) Exothermic reaction
1 Place about 5 cm? of hydrochloric acid in a test tube and record its
temperature.
Drop in a few pieces of magnesium.
3 When the reaction has stopped, take the temperature again.”

Remember...
The temperature of the water has risen because the reaction of
magnesium metal with hydrochloric acid is an exothermic reaction.

(41) Endothermic reaction

1 Place about 5 cm? of water in a test tube and record its temperature.
2 Add a few crystals of ammonium nitrate.
3 Stir gently until the crystals have dissolved.
4 ‘Take the temperature again.

156
 Remember...
The temperature of the mixture has fallen because dissolving
ammonium nitrate in water is an endothermic process.

Heat of reaction

The heat of reaction (AH) of a chemical reaction is the heat in kilojoules

released or absorbed when the number of moles of reactants indicated in
the balanced equation describing the reaction react completely.

The heat change depends on the amounts of reactants involved, which is

indicated by the balanced equation. If 1 mole of hydrogen gas burns in
oxygen to form water:

Hq) =: 1720 5g) = H,0.)

242 kilojoules of heat are produced. As this is an exothermic reaction, the

AH is negative because heat energy has been lost from the chemical
reactants to the surroundings, i.e. AH = —242 kJ mol™!.

For endothermic reactions, AH is positive because the chemical reactants

are gaining energy from the surroundings. For example, to break 1 mole of
water in the liquid state into hydrogen and oxygen gas:

HO) > Hig) + 1720 9,4)

286 kilojoules are required, i.e. AH = +286 kJ mol”.

Example 14.1
When 200 cm? of 1 M nitric acid solution (HNO3) react with 200 cm? of 1 M
potassium hydroxide solution (KOH), the temperature rises by 6.7 Kelvins.
Calculate the heat of reaction described by the equation

HNO3/4q) + KOH
(aq)> KNO/,,) + H,0

Answer | :
The amount of heat produced in the reaction can be calculated from the formula:
Heat change = mc AT

where
m = the mass in kg of liquid heated by the reaction
c =the specific heat capacity of the liquid 3
_ AT= the rise in temperature
(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

As the reactants and products are very dilute solutions, it is assumed that their
densities and specific heat capacities are the same as water. Thus, 200 cm? of
each reacting solution can be taken to have a mass of 0.2 kilograms. The
specific heat capacity of water is 4.2 kJ kg"! K"!.

Heat change = mc AT
= 0.4% 42) Gan
= 11.256 ky.

The number of moles of HNO, in 200 cm? of 1 M nitric acid solution is

calculated as follows:

No. of moles = volume in litres x molarity

= 02%
= 0.2 moles

Since 0.2 moles of HNO; produce 11.256 kJ of heat when reacted with
KOH, 1 mole, the quantity indicated by the balanced equation, produces
56.28 kJ mol-!. In other words, the heat of reaction AH = —56.28 kJ mol},
the minus sign indicating that the reaction is exothermic, with heat being
produced.

Mandatory Experiment 14.1: Determination

of the heat of reaction of hydrochloric acid
with sodium hydroxide
The equation for the reaction is
HCliag) + NaOH aq) > NaCl.) + H,0
oes NY

Procedure ws
1 Place 50 cm? of the 1 M hydrochloric acid solution into a polystyrene cup.
2 Place 50 cm? of the 1 M sodium hydroxide solution into another
polystyrene cup.
3 Measure the temperature of each solution. The average of the two
temperatures is taken as the initial temperature. ;
Quickly add the base to the acid, stirring with an accurate thermometer.
Record the maximum temperature reached.
By subtraction find the rise in temperature.
8S
Sw)
ors
SS) Calculate the heat of reaction, i.e. the heat liberated when 1 mole of acid
reacts fully. A value close to -57 kJ mol! should be the result.
 ___FUELS AND HEATS OF REACTION 2 )
Bond energy
In chemical reactions, energy must be supplied to break bonds, and energy
is given out when new bonds are formed.

—
H O=0

These bonds are broken. These bonds are made.

Energy is taken in. Energy is given out.

Fig. 14.1 Bond energy

The energy needed to break bonds is called the bond energy.

Bond energy is the amount of energy in kJ needed to break 1 mole of

bonds of the same type, where all species are in the gaseous state.

The heat change for the reaction

CHa) me a 4H a)

is found to be 1664 kJ mol"!. In this reaction, four C — H bonds are broken,

and no other bonds are formed or broken. Thus, the C — H bond energy in
methane is a quarter of 1664 kJ mol"! since there are four bonds present in
each molecule, 1.e.

E(C — H) = ¥4(1664) = 416 kJ mol"!

The energy of a particular type of bond can vary depending on the molecule
that the bond is in.

Heat of combustion

The heat of combustion of a substance is the heat change in kilojoules

when 1 mole of the substance is completely burned in excess oxygen.

Example 14.2 »
When 1 mole of methane gas is burned completely in excess oxygen, carbon
dioxide and water vapour are formed and 890 kilojoules of heat energy are
released. Use this information to write an equation for the heat of combustion
of methane.
(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Answer
The balanced equation for the reaction is:

CH) + 2054) > CO,,4) + 2,0.)

Since 890 kilojoules of heat energy are released, the reaction is exothermic and
AH = -890 kJ mol'. The equation describes the complete combustion of
1 mole of methane, so the equation for the heat of combustion of methane is:

CHajg) 4g + 204q) > CO.%9) + 2H,O%q) AH == -890; kJ mol =i

Accurate values of heats of combustion can be obtained using a bomb

calorimeter.

The kilogram calorific value of a fuel is defined.as the heat

energy produced per kilogram of fuel.

Kilogram calorific values are also measured using a bomb calorimeter.

Heat of formation

The heat of formation is defined as the heat change in kilojoules when

1 mole of a substance is formed from its elements in their standard states.

The standard state of an element is its common form at 298 K and 101,325
Pa. For example, the standard state of hydrogen is H,,. and that of
magnesium is Mg...

Example 14.3 -
When 1 mole of carbon dioxide gas is formed fram its elements in their
standard states, 393 kilojoules of heat energy are released. Use this
information to write an equation for the heat of formation of carbon dioxide.

Answer Fs
The balanced equation for the reaction is:

C,,(s) + O 2g co 2(g)

Since 393 kilojoules of heat energy are produced, the reaction is exothermic
and AH = —393 kJ mol!. Carbon and oxygen are in their standard states, so
the heat of formation is -393 kJ mol! and the complete equation is:

G (s) + Oy(q) > COx.) AH = -393 kJ mol!

 ___FUELS AND HEATS OF REACTION2 of

Hess’s law
The law of conservation of energy states that energy cannot be
created or destroyed, but only changed from one form to another.

The Russian chemist GH Hess modified this law in

terms of heat changes.

GH Hess

Hess's law states that the heat change of a reaction depends

only on the initial and final states of the reaction and is
independent of the route by which the reaction may occur.

1
S,) + 120.4)

AH = -297kJ mol

AH = -395kJ mol"
$O,(4) + 20145)

$. = -98kJ mol
so, (s)

Fig. 14.2 An illustration of Hess’s law

Problems based on Hess’s law may be solved using the fact that for a
reaction described by a given equation, the heat of reaction equals the
sum of the heats of formation of the products of the reaction less the
sum of the heats of formation of the reactants of the reaction. In
symbols:
AH, = & AH,{products] — = AH,reactants]

Remember...
The heat of formation of an
element is O Kimo
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 14.4
Calculate the heat of combustion of ethane

C5 Hei) + 372044) > 200

3¢) + 3H,O, AH. = ?

given the heats of formation of ethane gas, carbon dioxide gas and liquid
water are -84.7 kJ mol-!, -393.5 kJ mol! and -285.8 kJ mol, respectively.

Answer

C5 Hei) + 37/204.) =< 2C05,4) + 3H,0w) AH. = ?

AH, = 2 AH,products] — © AH,[reactants]

=> AH(C,H,) = 2 x AH,(CO,) + 3 x AH(H,O) — AH(C,H,) - 3% x AHO.)
=> AH(C,H,) = 2 x (-393.5 kJ mol") + 3 x (-285.8 kJ mol’)
~ (-84.7 kJ mol!) — 3% «x (0 kJ mol!) ©
=> AHAC,H,) = ~1559.7 kK) mol!

In Example 14.5, the heat of combustion of one substance is given together

with all the heats of formation, except the one required to be calculated.

Example 14.5
The heat of combustion of propane is —2220 kJ mol"! and the heats of
formation of carbon dioxide gas and liquid water are -393.5 kJ mol! and
285.8 kJ mol’, respectively. Calculate the heat of formation of propane.

Answer
The equation for the heat of combustion of propaneis

gq) + 503g) > 3COxq) + 4H 09 AH, = -2220 kJ moll

C3H
AH, = & AH,products] — = AH,{reactants]
=> — AH(C3Hg) = 3 x AH(CO,) + 4 x AH,(H,0)
— AH,(C3Hg) — 5 x AH,(O,)
= -2220 kJ mol! = 3 x (-395.5 kJ mol') + 4 x (-285.8 kJ mol-!)
— AH{C3H,) — 5 x (0 kJ mol"
= -2220 kJ mol"! = -1186.5 — 1143.2 — AH,(C,H,) = 0
=> AH (C3H,) = -1186.5 — 1143.2 + 2220
=> AH(C3H,) = —109.7 kJ mol!

Oil refining and its products

When crude oil is brought to an oil refinery, the many compounds in the
crude oil mixture are separated according to their different boiling points.
This is done in a process of fractionation or fractional distillation. Fractional
 FUELS AND HEATS OF REACTION 2

distillation of crude oil results in a series of fractions, each consisting of a

mixture of hydrocarbons boiling within a given temperature range.

Table 14.1

Fraction Boiling range = Carbon atoms Typical uses

series per molecule
Refinery gas <300K 1-4 Liquefied
petroleum gas
(LPG)
Light gasoline 300-350K 5-8 Petrol
Naphtha 350-435K 8-10 Petrol and organic
chemicals
Kerosene 435-525K 10-14 Central heating
fuel, jet fuel
Gas oil 525-625K 14-19 Diesel fuel
Fuel oil and >625K >19 Power station fuel,
residue bitumen,
lubricating oil,
greases

Natural gas
Natural gas is a mixture consisting mostly of methane (CH, — at least
85%), ethane (C,H; — up to 10%), and smaller amounts of propane (C,H,)
and butane (C,H, ,). Trace amounts of other elements may also be present.
Natural gas is an extremely important fuel both for domestic and
industrial use.

Like LPG, natural gas is almost odourless. As both are highly inflammable
and explosive when mixed with air, undetected leaks present a serious
hazard. Very smelly organic sulfur compounds called mercaptans are added
to the gas so that leaks can be detected almost instantly by smell.

Petro! and the internal combustion engine

Petrol is a complex mixture of at least 100 different compounds, mostly
hydrocarbons. Most of these are branched-chain alkanes and some are
aromatic compounds.

When petrol is pumped into the engine of a vehicle — an internal

combustion engine — the petrol is first vaporised and then mixed with air.
The petrol/air mixture is compressed by the piston and then ignited by a
spark from the spark plug and burned. The gases produced by the
combustion reaction expand and cause the piston to move. In effect,
a | LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

kinetic energy is produced and this is transmitted to the wheels to make

the car move.

The more gases are compressed, the more they tend to heat up. Sometimes
this causes ignition before the spark is produced. This is intended in a diesel
engine, where there is no spark plug, but in a petrol engine the occurrence
is called auto-ignition or knocking or pinking. This is quite a problem as
it can cause loss of power, with obvious danger, or damage to the engine.

Auto-ignition is ignition in an internal combustion engine

before a spark is produced.

Octane numbers

The octane number (or octane rating) is a measure of the

tendency of a fuel to auto-ignite or cause knocking.

The lower the octane rating, the more likely it is that auto-ignition will
occur. Clearly, high-octane fuels are more desirable.

In devising a scale, two compounds were chosen, heptane (C,H,,) and

2,2,4-trimethylpentane (CI 1,C(CE 1) CI LCI 1(C} 1,)CI 1,). Heptane has a
high tendency to auto-ignite, so it was given an octane number of 0. On the
other hand, 2,2,4-trimethylpentane has a low tendency to auto-ignite, so it
was given a rating of 100.
H CH; HCH; H
Leclitnaalt smite ul
H—c—cC—C—cC—cC—R
Pie ee arias
Ho cHeorrnatH: aH
2,2,4-trimethylpentane
Octane number = 100

H H H H H H H
Luss pebartiteg hy titel
H C C C= c C G H
ee Ae mH reel aaa 24,
H H H H H H H
Heptane
Octane number = 0

Fig. 14.3
A mixture of these two compounds containing 95 per cent 2,2,4-
trimethylpentane is said to have an octane number of 95 (2,2,4-
trimethylpentane is also known as iso-octane, hence the terms ‘octane
numbers’ or ‘octane rating’).
 FUELS AND HEATS OF REACTION 2 © w

Petrol with an identical tendency to auto-ignite as this mixture, under the

same conditions, would thus also be given an octane rating of 95. A
compound less likely to auto-ignite than pure iso-octane would have an
octane number of more than 100.

Additives
One method of preventing knocking is the use of additives in petrol
manufacture. Two types of additive have been in use in recent decades, lead
compounds and oxygenates.

Lead compounds work by preventing the type of reactions that cause auto-
ignition. However, the lead compounds present in exhaust fumes are toxic.
Leaded petrol also became unsuitable for use in modern vehicles because the
lead compounds acted as catalytic poisons in the catalytic converters of
vehicles. Leaded petrol has been phased out in many countries, and has been
banned in Ireland since 2000.

Adding compounds called oxygenates prevents knocking by raising the

octane number of the fuel. They have the added benefit of causing less
pollution because, apart from not containing lead, they produce lower levels
of carbon monoxide when they burn. The most commonly used oxygenate
is MTBE (methyl tertiary butyl ether). Its octane rating is 118.

CH;

WCC — 0 CH

CH;
MTBE
Octane number = 118

Fig. 14.4

High-octane compounds
Apart from additives, using a mixture of high-octane compounds in petrol
manufacture also prevents knocking. Compounds with certain structural
features are found to have high-octane numbers, which make them suitable
for petrol manufacture. These features are: a high degree of branching,
short-chain length and the existence of rings in the molecule.

[somerisation
When certain compounds are heated in the presence of a suitable catalyst, a
different structural isomer of the particular compound is formed. Pentane
(C5H,,) is a straight chain alkane that has an octane number of 62. If
pentane is heated in the presence of a suitable catalyst, the chain breaks and
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

the fragments rejoin to form a branched compound, 2-methylbutane

(CH,CH(CH,)CH,CH,).

This compound has the same molecular formula as pentane, so they are
structural isomers of each other. Since the product has an octane number of
93, it is a much more suitable component of petrol than the original
pentane.

Dehydrocyclisation
This process involves the formation of a ring compound, accompanied by
the removal of hydrogen gas, which is a valuable by-product. A straight
chain alkane such as hexane (C,H, ,), which has an octane number of 25, is
heated in the presence of a suitable catalyst. The catalyst causes the hexane
to change to cyclohexane, which is a cycloalkane, that is, an alkane
containing a carbon ring.

This step alone causes an increase in octane number from the 25 of hexane
to the 83 of cyclohexane.

The catalyst then causes the cycloalkane to change further to an aromatic

compound, benzene, which has an octane number greater than 100.

In terms of octane numbers, the overall effect is to increase from 25 to a

number greater than 100.

Catalytic cracking
This process involves taking heavy oil such as kerosene or diesel and heating
it to a high temperature in the presence of a catalyst. The large molecule
breaks down into several smaller ones: some saturated, some unsaturated.
For example:

| i | H H ai nbs dnb on! > Sal H H

(es ee ee
ini C=—¢€ c G (c C C E C G C H
PPT EE aD Ay MR Ge
nt Int dat Ta H i Sheen Hitt aH

i CH; | a | ieee CH; H

Lette eotae
H Cc CG cag H + H iC 1 C iG H
(ne et ee Lae | oul
ine dh tT H a aa
2,4-dimethylpentane 2-methylbut-1-ene

Fig. 14.5 An example of catalytic cracking

 FUELS AND HEATS OF REACTION2
The unsaturated products are used as feedstock for the polymer industry.
The saturated products are usually high-octane branched-chain alkanes
suitable for making petrol.

Hydrogen
Hydrogen (H,) is a colourless, odourless gas, which is almost insoluble in
water. It is the least dense of all gases.

Hydrogen is used in large quantities in the chemical industry in processes

such as the manufacture of ammonia, the hydrogenation of vegetable oils to
make saturated fats, and the manufacture of hydrochloric acid.

Hydrogen has great potential as a motor fuel. It burns more efficiently than
petrol and is non-polluting. Water is the only product, apart from trace
quantities of nitrogen oxides.

Steam reforming
Natural gas is an important industrial source of hydrogen. Methane, the
major component of natural gas, is reacted with steam:

CHa) + HO.) = CO.) +- 3H5(9)

The mixture is then reacted with more steam and the carbon monoxide is
oxidised to carbon dioxide, producing more hydrogen in the process:
CO) + HO.) == CO34) 4 H99)

The process successfully converts about 70 per cent of the methane to

hydrogen.

Electrolysis of water
Electrolysis of water is an expensive method of producing hydrogen as it
uses a large amount of electricity. Pure water itself is not an electrolyte, that
is, it will not conduct electricity. Instead, dilute sulfuric acid is added. Inert
electrodes of platinum or carbon are used. Hydrogen is liberated at the
negative electrode, the cathode, while oxygen is liberated at the positive
electrode, the anode. The overall reaction 1s
»
H50y) > Hy) + 1Y20(g)

Key Points
An exothermic reaction is a reaction that gives out heat to the Now
~ surroundings.
An endothermic reaction is a reaction that takes in heat from the
_ surroundings.
(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The heat of reaction (AH) of a chemical reaction is the heat in kilojoules

released or absorbed when the number of moles of reactants indicated in
the balanced equation describing the reaction react completely.
Bond energy is the amount of energy in kJ needed to break 1 mole of
bonds of the same type, where all species are in the gaseous state.
The heat of combustion of a substance is the heat change in kilojoules
when 1 mole of the substance is completely burned in excess oxygen.
The kilogram calorific value of a fuel is defined as the heat energy
produced per kilogram of fuel.
The heat of formation is defined as the héat change in kilojoules when
1 mole of a substance is formed from its elements in their standard states.
The law of conservation of energy states that energy cannot be created or
destroyed, but only changed from one form to another.
Hess's law states that the heat change of a reaction depends only on the
initial and final states of the reaction and is independent of the route by
which the reaction may occur.
Auto-ignition is ignition in an internal combustion engine before a spark is
produced.
The octane number {or octane rating) is a measure of the tendency of a
fuel to auto-ignite or cause knocking.

Your revision notes

 CHAPTER 15
Rates of Reaction

ee 8Topics Covered in this Chapter |

@ Rates of reaction
@ Average and instantaneous rates =
@ Factors affecting reaction rates: concentration, temperature, particle
" size, nature of reactants, catalyst
Pollution caused by car engines
Catalytic converters
Activation energy
Theories of catalysis
Demonstrations involving catalysts

Rates of reaction
The rate of a chemical reaction is a measure of how q quickly i the reaction
proceeds. It may be defined as the change in concentration in unit time of
any one reactant or product, i.e.
Change in concentration
Rate =
Time taken

The rate of a chemical reaction is the change in concentration in

unit time of any one reactant or product. —

Mandatory Experiment 15.1: Monitoring the

rate of production of oxygen from hydrogen
peroxide, using manganese dioxide as a catalyst
Hydrogen peroxide decomposes into water and oxygen as follows:

H,05") > H,0() + 22044)

Manganese dioxide acts as a suitable catalyst and, when it is added, the

reaction occurs at a measurable rate.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Procedure
iy Place 50-cun: is? 2 eon hydrogen peordenina cone flask
2 Weigh about 0.5 g manganese(IV) oxide into a small test tube. Suspend
the test tube in the conical flask using the thread. The manganese(IV)
oxide and the hydrogen peroxide should not come into contact until the
stop-clock is started.
Uo Fill the graduated cylinder with water from the trough, and invert it
onto the beehive shelf.
Assemble the apparatus for the collection of the oxygen produced, by
displacement of water. ;
Bring the manganese(IV) oxide into contact with the hydrogen peroxide
by loosening the stopper sufficiently to allow the thread to fall into the
flask. Shake vigorously, starting the stop-clock as the manganese(IV)
oxide comes into contact with the hydrogen peroxide solution. Record
the volume of oxygen in the graduated cylinder every 30 seconds.
Draw a graph of total volume of oxygen against time, putting time on
the horizontal axis.

=| _— Graduated cylinder

Thread—_

Water

Manganese(IV) oxide — Hydrogen peroxide

in small test tube solution

Fig. 15.1

Example 15.1
When a hydrogen peroxide (H,O,) solution was decomposed in the presence
of a suitable catalyst, the oxygen gas produced was collected and its volume
measured every three minutes until the reaction was complete. The data
obtained are shown in the table.

Time (mins) 0 3 6 9 12 15 18 21
Volume (cm?) 0 30 45 5S 57 59 60 60

(i) Give the name and formula of a suitable catalyst for this reaction.
(ii) Plot a graph of the volume of oxygen gas collected against time.

(continued)
aS an einem ___RATES OFREACTION
(iii) Is the rate of reaction faster after 3 minute or after 9 minutes? Justify
your answer from the shape of the graph.
(iv) What volume of oxygen had been collected after 7.5 minutes?
(v) How long did it take to collect exactly 40 cm3?
(vi) After how many minutes was the reaction finished? Explain your answer.

Answer
(i) Manganese dioxide (MnO,).
(ii) 0 Ea

(cm?)
Volume

0 5 10 15 20 25
Time (minutes)

Fig. 15.2
(iii) The rate of reaction is faster after 3 minutes. The slope of the graph is a
measure of the rate at any point in time. The slope of the graph is much
steeper at 3 minutes than it is at 9 minutes, so it can be deduced that the
rate is faster at 3 minutes.
(iv) 49.7 cm?.
(v) 4.8 minutes (4 minutes 48 seconds).
(vi) The reaction was finished after 18 minutes because no further oxygen
was produced after this time.

Average and instantaneous rates

In Example 15.1, 60 cm? of oxygen gas were produced in 18 minutes. The
average rate of production of oxygen is volume/time = 60 cm?/ 18 minutes =
3.3 cm? min-!. However, the rate is not constant throughout the reaction. For
example, the average rate for the first 3 minutes is volume/time = 30 cm?/ 3
minutes = 10 cm? min™!.
~

The instantaneous rate of reaction is the rate at a particular

point in time during the reaction.

The rate at a particular point in time is known as the instantaneous rate.

It can be found by drawing a tangent to the curve at the appropriate point
on the curve. The slope of the curve, which is calculated as shown in
Example 15.2, is a measure of the reaction rate.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 15.2
In the experiment described in Example 15.1, calculate the instantaneous rate
of reaction after 4.5 minutes.

Answer
(i)

of
Volume
(cm3)
O,

3 6 9 12 ies 18 21
Time (minutes)

Fig. 15.3
(ii) A tangent to the curve is drawn at the point where time t = 4.5 minutes.
(iii) A right-angled triangle is drawn with the tangent as hypotenuse, and the
other two sides, of lengths At and Av, respectively, parallel to the
horizontal and vertical axes of the graph.
(iv) The angle @ equals the angle made by the tangent with the horizontal axis.
(v) Slope = tan 0 = Av/ At = 41.0/8.25 = 4.97 cm? min"!

Factors affecting reaction rates

There are a number of factors which can influence the rate of a chemical
reaction:
® Concentration of reactants
Temperature of the reaction
Particle size of solid reactants
Nature of reactants, i.e. whether ionic or covalent
Presence of a catalyst

Concentration of reactants
An increase in the concentration of the reactants usually increases the rate
of the reaction.

In the decomposition of hydrogen peroxide using manganese(IV) oxide as a

catalyst,

H,O5~ > HOW + 220444)

the more concentrated the peroxide solution, the more rapidly the oxygen
gas is produced. The peroxide concentration decreases as the reaction
proceeds, so the reaction rate decreases.
 __RATESOFREACTION [0
Temperature
An increase in temperature usually brings about an increase in reaction rate.

Mandatory Experiment 15.2: Studying the effects

on the reaction rate of (i) concentration and
(ii) temperature, using sodium thiosulfate
solution and hydrochloric acid
Sodium thiosulfate solution reacts with hydrochloric acid solution
according to the following equation:
2HCliagy + NazS,O3(4q) > 2ZNACI(aq) + SOz(aq) + Sh + HO
The pale yellow precipitate of sulfur formed gradually obscures a cross
marked on paper placed beneath the reaction flask. The time taken to
obscure the cross, which is inversely proportional to the rate of reaction,
depends on variables such as temperature and concentration.

(i) Effect of concentration

Preece
1 Place 100 cm? of a 0.1 M sodium thiosulfate solution in a conical flask.
2 Add 10 cm? of 3 M hydrochloric acid to the flask and swirl, while
starting the stop-clock at the same time.
3 Place the flask on a piece of white paper marked with a cross.
4 Stop the clock when the cross disappears completely and record the
time taken in seconds. Calculate the rate as the inverse of the time, i.e.
1/time (sec~!).
5 Repeat the experiment using 80 cm? of sodium thiosulfate solution
mixed with deionised water to make the volume up to 100 cm’.
6 Repeat step 5 using 60, 40 and 20 cm? of sodium thiosulfate solution,
respectively, in turn.
7 Draw a graph of reaction rate, 1.e. 1/time (vertical axis) against
concentration of thiosulfate solution (horizontal axis).

(ii)Effect of temperature
Procedure
1 Place 100 cm? of 0.05 M sodium thiosulfate solution into a conical flask
at room temperature.
2 Add 5 cm? of 3 M HCI, starting a stop-clock at the same time.
3 Swirl the flask immediately and place it on a piece of white paper
marked with a cross. Record the exact temperature of the contents of the
flask.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

4 Record the time in seconds taken for the cross to disappear. Calculate
the rate as the inverse of the time, i.e. 1/time (sec).
5 Repeat the experiment, heating the thiosulfate solution to temperatures
of approximately 30°C, 40°C, 50°C and 60°C, respectively (before
adding the HCl and taking the exact temperature).
6 Draw a graph of reaction rate, i.e. 1/time (vertical axis) against
temperature of reaction mixture (horizontal axis).

Particle size
In reactions where one of the reactants is a solid and the other reactant is a
liquid, the particle size of the solid has a marked effect on the rate of
reaction. The more finely divided the solid, the faster the reaction.

For example, in the reaction of marble (calcium carbonate) with dilute

hydrochloric acid solution, powdered marble reacts much more quickly
than marble chips.

Specified Demonstration: The effect on

reaction rate of particle size aa!
The reaction between calcium carbonate and dilute hydrochloric acid is
used in this demonstration:

CaCO, 3(s) + ZHClqq > CaCl + H,Oy) + CO 2(g)

Procedore
Place 5 g of powdered calcium carbonate in a conical flask.
Place 50 cm? of hydrochloric acid solution in a graduated cylinder.
NO
OW Pour the acid into the conical flask and swirl, starting a stop-clock as
the substances come into contact.
4 Stop the clock when the reaction has ended, i.e. when gas bubbles are
no longer produced. Record the reaction time.
1) Repeat steps 1—4, this time using 5 g of marble chips.
6 It will be found that the time taken for the powdered calcium carbonate to
react completely will be less than that for the marble chips.

Dust explosions |
Dust explosions are a hazard in coalmines, grain silos and other industrial
situations. Any solid material that can burn in air will do so at a rate that
increases with increased surface area. If the heat released is sufficiently
great, then an explosion will occur.
 __ RATES OF REACTION, =f

Nature of reactants
Reactions of covalent compounds are generally slow. In this type of
reaction, bonds have to be broken before new bonds are formed. For
example, water vapour and carbon dioxide are formed in a reaction between
methane gas and oxygen gas.

In this case, C — H bonds and O = O bonds must be broken before the

O — H bonds in water vapour and C = O bonds in carbon dioxide can be
formed.

Reactions of ionic compounds normally take place in aqueous solution.

When an ionic compound is being dissolved in water, the constituent ions
are pulled apart by water molecules and surrounded by them.

Thus, when two reacting solutions are mixed, the bonds are already broken,
and so when the ions collide they react. For example:

Ag*... + aa) = AgCl,.)

Catalysts
A catalyst is a substance that alters the rate of a chemical reaction
but is not consumed in the reaction.

Catalysts are often transition metals or their compounds, which speed up

reactions in solution or in the gas phase. Catalysts work by lowering the
energy needed to start a reaction — the activation energy — so the operating
temperature can be lowered and costs reduced as a result.

In reactions such as the decomposition of hydrogen peroxide into oxygen

and water, using manganese(IV) dioxide as a catalyst, the catalyst is in a
different physical state (phase) to the reactant. This type of catalysis is
heterogeneous.

A heterogeneous catalyst is a catalyst that is in a different

: phase to the reactants.

In homogeneous catalysis, the catalyst is in the same physical state (phase)

as the reactants. For example, aqueous potassium iodide solution catalyses
the decomposition of hydrogen peroxide to water and oxygen:
Kliag)
1
HO raq) > 2A + 20926)
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

A homogeneous catalyst is a catalyst that is in the

same phase as the reactants.

Enzymes act as homogeneous catalysts in living systems. Examples include

peroxidase, an enzyme found in the livers of mammals, and zymase, a series
of enzymes found in microscopic fungi called yeasts. Zymase helps control
the fermentation of sugar to alcohol in the production of alcoholic drinks.

Autocatalysis occurs when a product of a reaction increases the rate of the

reaction. For example, in the reduction of manganate(VII) ions

MnO4 faq) + 8H *faqy + Soave > MnP ay + 5Fe?* 4) + 4H,0w

the Mn** (aq) 1ONS produced catalyse the reaction. The first few drops of the
purple MnO," On solution added to the Fe?* (aa) solution are decolourised
slowly, while subsequent drops are Hecolotdced rapidly. The Mn?* (aq)
formed by the initial slow reaction catalyses the subsequent reaction, the
rate of which is increased.

Specified Demonstration: The effect on reaction

rate of a catalyst
Hydrogen peroxide decomposes into water and oxygen gas. The reaction
proceeds extremely slowly in the absence of a catalyst. However, if a few
grains of manganese dioxide are added, bubbles of gas are immediately
formed.
2H,O05") > Ong)2(g) + 2H,0y)

Procedure *
1 piace bow 25 cm? of Byclroeen peroxide solution in the beaker.
Note that there is no significant formation of bubbles.
2 Using the spatula, sprinkle a few grains of manganese dioxide on
the surface of the hydrogen peroxide. Note that a vigorous reaction
takes place, with the production of bubbles of gas.~

Pollution caused by car engines

Carbon monoxide is formed by the incomplete combustion of petrol
vapour:

CgH 1gq) + 8205/4) > 8CO,,) + 9H, 0()

This is the reason why running a car engine in an enclosed space may be
(8 lethal, as carbon monoxide poisoning may result.
 ___RATESOF REACTION_ a
is

Nitrogen monoxide is formed when the spark from the spark plug causes
the petrol/air mixture to explode. The very high temperature causes
nitrogen and oxygen from the air in the mixture to react:

N, (ait 2(g)
ogi 2NOq)

Nitrogen monoxide reacts readily with oxygen to form nitrogen dioxide,

which in turn reacts with water and oxygen to form nitric acid:

2NOQq + Oy)2(g) > ZNOx.

4NO, (Vig 2H,0() +505) > 4HNO3/4)

These’ reactions occurring in the atmosphere cause acid rain. In sunlight,

nitrogen dioxide also reacts with oxygen or hydrocarbons to form an
irritating photochemical smog.

Incomplete combustion of petrol vapour can also result in the emission of

unburnt hydrocarbons, which can act as greenhouse gases.

Catalytic converters
The catalytic converters in car exhaust systems help to reduce the emission
of gases such as nitrogen monoxide, carbon monoxide and hydrocarbons.

The catalyst is a mixture of transition metals — platinum, rhodium and

palladium — in the form of a very fine powder. The catalyst is spread in a
very thin layer over a ceramic support material full of tiny holes that
provide a large surface area.

Exhaust gases containing

unburned fuel, carbon monoxide,
nitrogen oxides and air

Catalyst

Carbon dioxide, Solid support

water and nitrogen
Catalyst coating

Fig. 15.4 A catalytic converter

LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

As the catalyst is solid and the reactants are gaseous, this is an example of
heterogeneous catalysis.

Reactions catalysed
Carbon Prono is converted into carbon didcide sy reaction in oye:
CO + 2202) > C034)

Carbon monoxide is also converted into carbon dioxide in a reaction with

nitrogen monoxide:
2CO iq)+ ZNOpw) > 2CO4p) + Noig)
This reaction has the advantage of reducing the pollutant nitrogen
monoxide to nitrogen gas. By catalysing both of these reactions, the
converter removes two pollutants quite effectively from exhaust gases.

Unburnt hydrocarbons are also oxidised to carbon dioxide and water, e.g.
octane:
CeH 9) +127205(,) > 8CO44)+ AZO)

Environmental benefits ofcatalytic converters

e Pedicron or emissions of carbon monoxide,
® Reduction of emissions of nitrogen oxides, removing one cause of acid
rain, and reducing the amount of photochemical smog in large cities.
@ Reduction of emissions of other toxic gases such as unburnt
hydrocarbons.

Activation energy
Molecules must collide with sufficient energy for reaction to take-place. The
minimum energy needed is called the activation energy (E,), measured in i
kilojoules per mole (kJ mol’).

Activation energy is the minimum energy with which particles

need to collide to cause a reaction. -~

If the reactants collide with energy at least equal to the activation energy,
the collision is successful and products will form. Otherwise the molecules
will simply rebound without reaction.
ee CRATES
OF REACTION’
.

ie ! | Activation | |
O ane energy i aa
E P
2 eee a aaSeeeEaEE
=S ' ti andBEECH
and-D) sia | as aaa
g EAD thi ie 3 8H a | AH. is negative. I
w Ec OT
Ae si

reser Products
i 1H:0.and co,
Reaction pathway —>

Fig. 15.5 Energy profile diagram for an exothermic reaction

The difference between the energy of the reactants and the energy of the
products is the heat of reaction (AH) and it has a negative value. The
activation energy (E,) is shown as a hump that must be overcome for the
reaction to proceed.

ea=
ss a
3!

iat

ere
Leber
Reaction pathway —>

Fig. 15.6 Energy profile diagram for an endothermic reaction

The heat of reaction (AH) in this case has a positive value. The activation
energy (E,) is again shown as a hump that must be overcome for the
reaction to proceed.

Influence oftemperature on reaction rate

Seeeeneosaeseosese

Reactions occur faster at res temperatures. che fiche iis nese

the greater is the energy of the molecules and the greater their average speed.
This has two consequences, each of which increases the rate of reaction.
(a) The number of collisions per second is increased.
(b) Each collision is more energetic, and a higher proportion of collisions
have the necessary activation energy for reaction to occur.

Factor (b) is much more significant in increasing reaction rate than (a).

Theories of catalysis
Catalysts work by providing an alternative reaction route with lower
activation energy. ; wn)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

“naatalysed ited nessa

reaction
Leepeli
inn reaction co

Reactants

mol—')
(kJ
Energy
—>

Reaction pathway —>

Fig. 15.7 A catalyst lowers the activation energy for the reaction

By lowering the activation energy, a catalyst can make it possible to carry

out a reaction at a lower temperature, with consequent savings in energy
costs.

Intermediate formation theory of catalysis

Homogeneous, alee sometimes work by reacting with reactants to ou
unstable intermediate products. These intermediates decompose readily,
forming products and regenerating the catalyst.

Specified Demonstration: Oxidation of potassium

sodium tartrate by hydrogen peroxide, catalysed
by cobalt(t!) salts
Potassium sodium tartrate tons (C,H. Oe -) are oxidised by hydrogen
peroxide to carbon dioxide and water. ;

Gath O.2" + HO, => COn te Hye) ‘

The reaction is catalysed by Co** ions.

At the start of the reaction, the mixture will have-the pink colour of
the cobalt(II) ions. During the course of the reaction, which is
indicated by vigorous bubbling, a green colour, that of an intermediate
complex, will be seen. However, as the reaction nears its conclusion,
the pink colour will be restored showing that the catalyst is being
regenerated.
 ___RATES
OF REACTION (OL
Procedore
1 Decne aBCuE eeg etsagent am tartrate in565 cm? ue water,
which has been heated to about 50°C.
2 Dissolve about 0.2 g of cobalt chloride crystals in water and add this to
the potassium sodium tartrate solution.
3 Add 20 cm? of 100 volume hydrogen peroxide.
4 The initial pink colour changes to green, before reverting to pink.

Surface adsorption theory of catalysis

The Be rmedeons catalysis of gaseous reactions ies Penisd is Belercd to
involve adsorption. This is where some sort of bond or attachment is
formed between one or more of the reactants and the surface of the
catalyst.

A given catalyst has a number of active sites at which the reactants may
adsorb. The bond must be strong enough to hold the reactants to the surface
of the catalyst, but weak enough to break and release the products, so
making sites available for more reactants to adsorb.

The addition reaction of hydrogen to ethene, forming ethane, is catalysed

by nickel. An ethene molecule is believed to adsorb onto the surface of the
nickel, as does a molecule of hydrogen, which splits into two atoms in the
process. The two hydrogen atoms add on in turn to the ethene, forming a
molecule of ethane, which then desorbs from the nickel surface.

Catalytic poisons
Catalysts can be poisoned sOs that Abe noeionees foncconeatt full ea
In heterogeneous catalysis, the particles that poison the catalyst, e.g. lead,
arsenic and compounds of sulfur, are adsorbed more strongly onto the
catalyst surface than the actual reactant particles. This is the reason why cars
fitted with catalytic converters cannot use leaded petrol. The lead atoms
bond strongly to the platinum/rhodium surface of the converter, poisoning
it and making it ineffective.

Catalytic poisons can block the active sites of enzymes. This can inhibit
vital biochemical reactions.

Specified Demonstration: Demonstration

of the oxidation of methanol using a hot
platinum catalyst
This isa example of heterogeneous catalysis, where methanol, an alcohol,
is oxidised to methanal, an aldehyde. The oxygen in the air removes
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

hydrogen atoms from the methanol. The rate is extremely slow in the
absence of a catalyst. However, in the presence of hot platinum, the reaction
proceeds rapidly and is so exothermic that the wire glows.

hot Pt catalyst
2CH,0OH + 0, ——® = 2HCHO + 2H,0
Methanol Methanal

1
with the cardboard insert as in Figure 15.8.
Warm slowly to about 60°C on a hot plate.
Ov Place the flask on a heat-resistant mat.
Heat a spiral of platinum wire to red heat in a Bunsen flame (making
sure that the naked flame is well away from the methanol).
Quickly lower the spiral into the flask on one side of the cardboard
insert, using a piece of nichrome wire to suspend it from the neck of
the conical flask.
The spiral, which will have cooled to below red hot during the
transfer, should begin to glow again.
There may be a number of mild explosions.
These may become cyclic, i.e. the spiral glows, the mixture explodes,
the spiral cools, then heats up again until a further explosion occurs.
This should continue as long as there is a supply of methanol.
The card allows more air to flow in and allows the waste gases to be
swept away.

Aluminium-covered
cardboard for
chimney effect

Red hot platinum spiral

suspended by looping
one end of wire

Warmed flask

Methanol
 RATES OF REACTION

os Themate
ra aea chemical reaction is the change it
in concentration in
i aint
:~ time of any one reactant or product. .
@ The instantaneous rate of reaction is the rate at a Paes: point in time
~ during the reaction. :
A catalyst is a substance that alters the rate of a chemical reaction
r but iis
not consumed in the reaction.
A heterogeneous catalyst is a catalyst that isi ina different phase to >the
reactants. :
A homogeneous catalyst is a catalyst that is in ‘the same©phaseas s the
reactants. és 2 —
Activation energy is the minimum eneray with which partiesneedto
collide to cause a reaction. oe

Your revision notes

 (CHIAPTER 16
Organic Compounds

@@>° Topics Covered in this Chapter

Tetrahedral carbon
Chloroalkanes
Alcohols
Planar carbon
Aldehydes
Ketones
Carboxylic acids
Esters
Aromatic compounds
Organic natural products

Tetrahedral carbon

In saturated organic compounds, all of the carbon atoms are

tetrahedral.

In alkanes, chloroalkanes and alcohols, all of the carbon=atoms are

tetrahedral.

Chloroalkanes
A chloroalkane is an alkane in which one or more hydrogen atoms are
replaced with chlorine atoms.

The part of the alkane remaining after one hydrogen atom has been removed
is an alkyl group. For example, when a hydrogen atom is removed from
methane (CH), a methyl group (-CH,) remains.

Chloroalkanes are named after the alkane from which they are derived.
The prefix chloro— indicates the presence of a chlorine atom.

184
 ORGANIC COMPOUNDS

- Name of — Chemical Structural formula

ct : compound formula 2
| Chloromethane CHCl H
|
AG
|
Cl

2 Dichloromethane CEEch Cl
|
= GC}
|
H

3 Trichloromethane CHCl, Cl
|
HC — ¢
|
Cl

4 Tetrachloromethane CCl, ‘a
|
ch — Gi GC
|
Cl

Example 16.1
Name and draw the structural formulas of (i) CH,CICH,CI and (ii) CH,CCl,.

Answer
(i). ~CHL CICH,Cl
Since there are two chlorine atoms, the prefix di— is used, hence
dichloroethane. There is one chlorine atom on each of the two carbons,
so the numbers 1 and 2 are listed as a further prefix, to indicate the
chlorine positions. The full name is therefore 1,2-dichloroethane.

H H

Ha C— +0. ==

2 a @

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

(il) —CHLCCI |
Since there are three chlorine atoms, the prefix tri- is used, hence
trichloroethane. All three chlorine atoms are on the same carbon, which
is designated number 1, so as to give the lowest number to the position
of the chlorine atoms. The full name is therefore 1,1,1-trichloroethane.

a
nari
cl—C —C—H
peed.
Che eet

Physical state and properties

Chiereaieanes are onic in water. However, they are very sorte in
non-polar solvents such as cyclohexane and methylbenzene.

Because of the polarity of the carbon—chlorine bond, chloroalkanes have

higher boiling points than the corresponding alkanes. Most chloroalkanes
are liquids at room temperature, with just chloromethane and chloroethane
being gaseous.

Uses
HORAliaee areerenncanierdly reer as eats Hees es:chee (PRS of
polarity, they readily dissolve grease and oil and other substances that are
insoluble in water. For this reason, they have been used extensively in the
dry cleaning of clothes.

Alcohols
The alcohols form a homologous series of organic compounds, of general
formula C_\H,_,OH. All the alcohols possess a hydroxyl group (-OH) as
the functional group. The carbon atoms, including Cex bonded directly to
the hydroxyl group, are all tetrahedral.

Alcohols are named by replacing the —-e at the end of the corresponding
alkane name with —0/.
8 ee Laer al ORGANIC COMPOUNDS
Example 16.2
Write the name, chemical formula and structural formula of the alcohol
derived from ethane (CH,):

Answer
The name of the alcohol is ethanol. The formula is C,H,OH. The structural
formula is

mia
ee
H—C—C—OH
me ie

The position of the hydroxyl group on the carbon chain must be given when
the chain contains three or more carbons. In alcohols with the hydroxyl
group at the end of the carbon chain, the carbon attached to the hydroxyl
group will be bonded to one carbon atom. Such alcohols are classed as
primary alcohols.

Fig. 16.1 Primary alcohols

Propan-1l-ol is an example of a primary alcohol:

OH

Ol
25

i
| | |
c—c
C =

| ee
OH
Fig. 16.2 Secondary alcohols

Secondary alcohols, for example propan-2-ol, have two carbon atoms

attached to the carbon with the hydroxyl group.
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

ae
os —A—i
xmI—aA—tr=
OH H
Fig. 16.3 Propan-2-ol

Example 16.3 :
Write the name, chemical formula and structural formula of the secondary
alcohol containing four carbon atoms.

Answer
Since there are four carbon atoms in the chain, whichever of the middle two
carbon atoms is attached to the hydroxyl group is designated position 2. Thus,
the alcohol is named butan-2-ol. The chemical formula is

CH,CH(OH)CH,CH,
H H H H

oe
HoH On F
Butan—2-ol

Physical state and properties

Figure 16.4 shows that alcohols have higher boiling points than alkanes of
similar relative molecular mass. Methanol, ethanol and the isomers of
propanol and butanol are all liquids at room temperature.
400.

350h

300

250
(K)
point
Boiling

200

30 40 50 60 70 80

Relative molecular mass

Fig. 16.4 Alcohols have much higher boiling points than alkanes
188 of comparable relative molecular mass
 __ ORGANIC COMPOUNDS
The presence of the polar -OH group in alcohols results in hydrogen
bonding between neighbouring molecules. These strong hydrogen bonds
have to be broken before the alcohol boils, so more energy must be supplied
and the boiling point is correspondingly raised.

Wine and beer are mixtures of ethanol, water and some other substances.
The ethanol molecules and the water molecules mix completely because
hydrogen bonds form between the hydroxyl groups in ethanol and the
hydroxyl groups in water.

Methanol and propan-1-ol also mix with water in all proportions. However,
the solubility decreases as the hydrocarbon chain gets bigger and becomes
more significant.
a
Laboratory activity
The solubility of methanol and butan-1-ol, respectively, in cyclohexane
and water, respectively, can be investigated as a laboratory activity.
Equal volumes (about 5 cm*) of methanol and cyclohexane are added to
a test tube, which is then stoppered, shaken gently, unstoppered
carefully and allowed to stand for a few minutes.

The presence of separate layers would indicate that methanol is insoluble

in cyclohexane; since no layers are evident, methanol is soluble in
cyclohexane. The activity can be repeated for methanol and water,
butan-1-ol and cyclohexane, and butan-1-ol and water. Butan-1-ol will
be found to be only sparingly soluble in water, but quite soluble in
cyclohexane. Methanol will dissolve readily in water.

Occurrence and uses

Most of the world’s supply of ethanol is made by the hydration of ethene.
However, the ethanol in alcoholic drinks is made by fermentation of sugars
in fruits such as grapes, as in wine-making. In fermentation, enzymes in
yeast break down the sugar to give carbon dioxide and ethanol.
: CgH,
20 6(aq) — 2C,H,OHq) + 2003.)

Fermentation is used in the brewing industry to make beer and in the

distilling industry to make spirits.

Ethanol is used extensively as a solvent for paints, glues, perfumes and

aftershaves. It is the major component of methylated spirits. However, a
small amount of methanol, which is poisonous, and a dye are added to the
ethanol to make it undrinkable. Methanol used in this way is said to be a
denaturing agent.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Planar carbon
Planar carbon atoms feature in a number of homologous series — those
whose compounds have a carbon-carbon (C = C) or carbon—oxygen (C = O)
double bond. The atoms in the double bond are planar, although other
carbon atoms in the molecule may be tetrahedral. The presence of a double
bond means that these compounds are unsaturated.

All compounds of the homologous series of alkenes, aldehydes, ketones,

carboxylic acids, esters and aromatic compounds possess one or more planar
carbon atoms.

Aldehydes
Aldehydes form a homologous series of compounds, of general formula
C.H,,,,,;CHO. All aldehydes contain the carbonyl group, which consists of
an oxygen atom attached to a carbon atom by a polar double covalent bond,
C =O. In aldehydes, there is always a hydrogen atom bonded to the carbonyl
carbon. The carbonyl carbon is a planar carbon atom. The functional group of
the aldehydes is -CHO.

\
O
Fig. 16.5 The carbonyl group

Aldehydes:are named by replacing the —e¢ at the end of the corresponding

alkane name with —a/.

Example 16.4 :
Write the name, chemical formula and structural formula of the aldehyde
containing three carbon atoms. y

Answer
The corresponding alkane is propane, CH;CH,CH3. The-name of the aldehyde
is therefore propanal. The formula is CH;CH,CHO. The structural formula is

aE ak
Va

(ee
ie al
Bd
A
ae
 ORGANIC COMPOUNDS
Physicalsateaiproperties
The boner sen double Bend: (C= On inwire coaatadbesana isPetite
polar. As a result, dipole-dipole attractions exist between adjacent aldehyde
molecules. This leads to boiling points that are higher than those of the
alkanes of similar relative molecular mass, but lower than those of
comparable alcohols. Apart from methanal, which is a gas at room
temperature, the other lower members of the aldehyde series are liquids.

The polarity of the carbon—oxygen double bond (C = O) means that water

molecules can form hydrogen bonds with the carbonyl group.
Consequently, the lower aldehydes dissolve in water. Aldehydes are soluble
in non-polar solvents such as cyclohexane.

Laboratory activity
Investigate the solubility of ethanal in cyclohexane and water,
respectively, in a manner similar to that described for methanol and
butan-1l-ol. Ethanal will be found to be soluble in both solvents.

Occurrence and uses

Beaealdchydet is Pound in almond kernels arid contnpntes to ree Tata
of this fruit.

Fig. 16.6 Benzaldehyde

Ketones
Like aldehydes, all ketones contain the carbonyl group (C = O). But unlike
aldehydes, the carbonyl group is in the middle of a carbon chain, which
means that there cannot be a hydrogen atom bonded to the carbonyl carbon.
The functional group of the ketones is C = O.

Ketones are named by replacing the —¢ at the end of the corresponding

alkane name with —one. Given that a ketone consists of two alkyl groups as
well as the carbonyl group, there must be at least three carbons present.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 16.5
Write the name, chemical formula and structural formula of the ketone
containing three carbon atoms.

Answer
The corresponding alkane is propane, CH3;CH,CH3.
The name of the ketone is therefore propanone. The formula is CH;COCH3.
The structural formula is

H He.
| |
H c G E H
Logon
H O H
Propanone

Physical state and properties

Ketones have similar physical properties to aldehydes, due to the influence
of the polar carbonyl group. The lower ketones are liquids at room
temperature and are soluble in water. All ketones are soluble in organic
solvents, and ketones have higher boiling points than alkanes of similar
relative molecular mass.

Laboratory activity
Investigate the solubility of propanone in cyclohexane and water,
respectively, in a manner similar to that described for methanol and
butan-1l-ol. Propanone will be found to be soluble in both solvents.

Uses .
Propanone is widely used as a solvent and has been used in nail varnish
remover.

Carboxylic acids
Carboxylic acids form a homologous series O
of compounds, of general formula reek VA
GH. OOH. ~The earboxyl = sroup <<“
(-COOH) is the functional group of OH
carboxylic acids. The structural formula of Fig. 16.7 The carboxyl group
the carboxyl group is shown in Figure 16.7.
The carboxyl carbon atom is a planar carbon.

Carboxylic acids are named by replacing the —e at the end of the

corresponding alkane name with —ozc acid.
 ORGANIC COMPOUNDS

Example 16.6
Write the name, chemical formula and structural formula of the carboxylic acid
containing three carbon atoms.

Answer
The corresponding alkane is propane, CH3CH,CH3. The name of the carboxylic
acid is propanoic acid. The chemical formula is CH3;CH,COOH. The structural
formula is

Physical state and properties

The lower eabaryte acids are eolenrless tame tonal, wen ae or
distinctive smells. Boiling points are higher even than those of alcohols of
similar relative molecular mass. These relatively high boiling points result
from the formation of dimers, where two carboxylic acid molecules are held
together by two hydrogen bonds.
yo a ee
== C—R_ R=alkyl group or H
YA
a ae 0”

Fig. 16.8

Hydrogen bonding can also occur between water molecules and the lower
carboxylic acids. As a result, acids containing up to four carbon atoms are
highly soluble in water.

Laboratory activity
Investigate the solubility of ethanoic acid in cyclohexane and water,
respectively, in a manner similar to that described for methanol and
butan-1l-ol. Ethanoic acid will be found to be soluble in both solvents.

Occurrence and uses

Teenie Tan (HCOOH) i is an irritanteaia ee ee By some ants ae is se
found in nettles. Ethanoic acid (CH,COOH) iis the principal acid found in
vinegar. Ethanoic acid is also used in the manufacture of cellulose acetate,
which is used in lacquers, varnishes, photographic film, non-shatter glass and
as rayon fibre.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Propanoic acid (CH,CH,COOH), benzoic acid (C,H,COOH) and some of

their salts are used in the preservation of food. Sodium benzoate is a
particularly widely used food preservative.

Esters
Esters are compounds derived from carboxylic acids. The formula of an ester
can be represented as RCOOR’, where R could be a hydrogen atom or an
alkyl group, and R’ is an alkyl group. All esters contain the ester linkage
— COO -, which contains a planar carbon.

The name of each ester has two parts: (1) the alkyl group derived from the
alcohol and (2) the name of the acid, with the ending —vic replaced by —oate.

Example 16.7
Write the name, chemical formula and structural formula derived from
methanoic acid (HCOOH) and ethanol (C,H.OH).

Answer rf »
The alcohol, ethanol, provides the first part of the name, ethyl. The carboxylic
acid, methanoic acid, provides the second part of the name, methanoate.
Thus, the ester is ethyl methanoate.

In writing the formula of the ester, the formula of the acid is written first with
the carboxyl hydrogen atom omitted, HCOO-. The alkyl group from the alcohol
is then added in place of the omitted hydrogen, so the completed formula is
HCOOC,H..

The structural formula is built up in the same way.

O

eae DROR Ga Gra

|
ie
Physical state and properties
Esters of lower relative aitalleeuleansmass arealitete The Hehicte easeyio
double bond (C = O) in the ester linkage is polar, leading to intermolecular
forces — but not hydrogen bonds — between adjacent ester molecules. Thus,
the boiling points of esters are similar to those of aldehydes and ketones of
similar relative molecular mass.
 ORGANIC COMPOUNDS
The polarity of the C = O group allows hydrogen bonding to occur with
water molecules, so esters with less than five carbon atoms are water soluble.
Esters are soluble in non-polar solvents.

Laboratory activity
Investigate the solubility of ethyl ethanoate in cyclohexane and water,
respectively, in a manner similar to that described for methanol and
butan-1-ol. Ethyl ethanoate will be found to be soluble in both solvents.

Occurrence and uses

eeeoveses

Members of the ester family have strong and often pleasant, fruity smells.
Many of them occur naturally and are responsible for the smells of flowers
and the flavour in fruits, e.g. mangos. Ethyl ethanoate is used as a solvent
for printing inks and paints. Fats and oils are naturally occurring esters of
long chain carboxylic acids.

Aromatic compounds
Compounds that contain a benzene ring are called aromatic compounds.
Benzene itself (C,H,) is the most important aromatic compound.

The benzene molecule consists of six carbon atoms joined to form a

hexagonal planar ring. Each carbon atom has four valence electrons. One of
these is used to bond with a hydrogen atom, and two others are used to form
sigma bonds with the carbon atoms on either side. This leaves one valence
electron, which is not involved in sigma bonding, on each carbon atom.

The six valence electrons not involved in sigma bonding are delocalised
in a pi type bond, which is spread around the six atoms in the ring.

The structure of benzene is H

represented as in Figure 16.9. The "
circle emphasises the delocalisation j—c¢ Sey
involved. | | or

fe
H—C C—H

H
Benzene, CgHe

Fig. 16.9
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Physical properties
Being non-polar, aromatic iycrcetnore do not cco to any extent in
water, but dissolve in non-polar solvents. Liquid aromatic hydrocarbons,
such as methylbenzene, are themselves good non-polar solvents, dissolving
non-polar solutes readily. Methylbenzene (C,H;CH,) is a widely used
industrial solvent.

Occurrence and uses

Some aromatic compounds, fata Hatsbenzene, are carcinogens. This means
that they are capable of causing cancer in humans. However, many other
aromatic compounds are non-carcinogenic. The common painkiller, aspirin,
is an example.

Aromatic compounds are in widespread use in a range of different

applications. They are used in the manufacture of dyes, detergents, garden
chemicals such as herbicides, and many medicines. The acid—base
indicators, phenolphthalein and methyl orange, are also aromatic
compounds.

Organic natural products

A natural product is any chemical produced in nature, either by plants or
by animals. Perfumes, dyes and medical potions can all be obtained in the
form of plant extracts. Examples of well-known natural products include
codeine, morphine, paracetamol, aspirin, quinine, nicotine, cocaine,
strychnine and caffeine.

Mandatory Experiment 16.1: The extraction of

clove oil from cloves by steam distillation
The technique allows substances to be distilled that, if heated on aoe own
to higher temperatures, might partially decompose.

Procedure .
1 Sen up the Ourck Ae anoaranie as inShe esne
2 Weigh out about 5—10 g of whole cloves, and place them in the pear-
shaped flask. Cover with a little warm water.
3 Connect the steam generator to the rest of the apparatus and heat it
to boiling point. Regulate the heat so that a constant supply of steam
is supplied to the pear-shaped flask. If Quickfit apparatus is used for
steam generation, use anti-bumping granules in the steam generator.
a ORGANIC COMPOUNDS
4 Monitor the level of boiling water in the steam generator during the
experiment, topping it up with hot water if necessary.
5 Collect the distillate. It should have a pale milky appearance. Note the
strong smell of clove oil.
6 When sufficient product has been collected, disconnect the steam
generator to prevent suck-back, and turn off the heat.

Steamf

Safety tube -

Steam
generator

Anti-bumping
Cloves
granules and water

Fig. 16.10

If desired, the clove oil may be separated from the water in the emulsion by
solvent extraction. The distillate is shaken up in a separating funnel with a
suitable solvent, such as cyclohexane. The non-polar clove oil will dissolve
in the cyclohexane, which is a non-polar solvent. The funnel is allowed to
stand until the aqueous and non-aqueous layers have separated. The layers
are run into separate beakers. The top layer is the solution of clove oil in
cyclohexane. The clove oil is recovered by evaporating off the cyclohexane
on a hot plate in a fume cupboard.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

In saturated organic compounds, all of the carbon atoms are sl

tetrahedral.
The alkanes form a homologous series of aliphatic hydrocarbons, of
general formula C,H,,,,,.
A chloroalkane is an alkane in which one or more hydrogen atoms are
replaced with chlorine atoms.
The alcohols form a homologous series of organic compounds, of general
formula C,H,,,,,OH.
The alkenes form a homologous series of aliphatic hydrocarbons, of
general formula C,H...
Aldehydes form a homologous series of compounds, of general formula
Cr HO.
Ketones contain the carbonyl group (C = O), located in the middle of a
carbon chain.
Carboxylic acids form a homologous series of compounds, of general
formula C,H,,,,;COOH.
The formula of an ester can be represented as RCOOR’, where R could be
a hydrogen atom or an alkyl group, and R’ is an alkyl! group.
Compounds that contain a benzene ring are called aromatic compounds,
e.g. benzene (C,H,).
All compounds of the homologous series of alkenes, aldehydes, ketones,
carboxylic acids, esters and aromatic compounds possess one or more
planar carbon atoms.

Your revision notes

 CHAPTER 17
Organic Chemical Reactions

@@® Topics Covered in this Chapter

Addition reactions
Reaction mechanism: ionic addition
Polymerisation
Substitution reactions: halogenation of alkanes
Reaction mechanism: free radical substitution
Other substitution reactions
Elimination reactions
Redox reactions
Reactions as acids
Organic synthesis

Addition reactions
An addition reaction is a reaction in which two molecules
add together to form one larger molecule.

Addition reactions are typical of unsaturated compounds, such as alkenes.

ae
\

ns
es AY >
Cas. ||
ans
Fig. 17.1
The planar, unsaturated alkene molecule changes into a tetrahedral,
saturated molecule in the process. In general, an addition reaction
involves a change in structure from planar to tetrahedral.

2 UTeon OF haeset
H H H H

Sy oe
C= +H, > (C G H
ea we heat | |

H H H H
Ethene Ethane
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Hydrogenation of double bonds is used in industry to convert vegetable

oils, which are unsaturated, into solid saturated materials used in margarine
and dairy spreads.

Adlon ofcHorne H H HH
ined —
C=C" 4 file = 16 H
y aes a
H H ae Peeta
1, 2-dichloroethane

This product, 1,2-dichloroethane, is used in industry to make chloroethene,

the raw material for the manufacture of the important plastic PVC.

Sur Clg TLL

H H H H
ES Aye | |
C=C +Br, aed G—'C—H
Pe cae | |
H H Br Br
1, 2-dibromoethane

H H H
~ —
Cac + HOH > E C—C=-H
“ie Pewee
H H Heanor
Ethanol

The addition of water is called a hydration reaction. i

(v) Addition of hydrogen chloride

H H oH
~ Dees,
C=C) He el C= G==H
|
H H a ol aL
Gl
Chloroethane

Stability of benzene
Benzene is a planar, unsaturated molecule. However, it does not readily take
part in addition reactions. It is a stable and relatively unreactive molecule. This
stability is caused by the very different delocalised pi bonding in benzene.
 ORGANIC CHEMICAL REACTIONS _ ee See

genta bg
Reaction mechanism: ionic addition

A reaction mechanism is a detailed step-by-step account of

how an overall reaction occurs.

The movement ofelectrons involved in bond breaking and bond making is

shown by using curved arrows (Fig. 17.2).

ae aaa
Movement of Movement of a
one electron pair of electrons

Fig. 17.2

Br’ f Br Br

Bicsbal aac? Birth eee a Br’

HGH, HC = CH HG ——GH,

The bromination of ethene is the example used to illustrate the mechanism

of an addition reaction.

The first step is the approach of a bromine molecule at right angles to the plane
of an ethene molecule. The electron-rich double bond induces polarity in the
bromine molecule. This results in a weak attraction between the partially
positive bromine atom (Br) and the double bond region of the ethene molecule.

Electron movement follows, causing the breaking of the bromine—bromine

bond. The bromide ion (Br) breaks away, while the bromonium ion (Br*)
bonds to the ethene molecule, forming a positively charged bridged structure.

In the last step of the reaction, the Br attacks the positively charged
intermediate from the opposite side to where the bridge is located.

Evidence for the ionic addition mechanism is found if sodium chloride

(NaCl) is added to the mixture for the reaction of bromine water, which
contains BrOH, to ethene. Mixed products result, including
2-bromoethanol, 1-bromo-2-chloroethane and 1,2-dibromoethane.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

H> 4
se, Lo H

C=C — H— C—C
A a | H
H
Carbonium-ion

Gh

H \ H Cl
i pup el lane
H— C—C ose? H ‘E g H

| \iy | |
H H H

Fig. 17.3 Mechanism of the reaction of ethene with hydrogen chioride

Gia

| 3 Cf
Ga 2 hi

Gis ch f cl
Paton set ee es,
eG a. C=C —— ‘C’—C—-H
en SS Ho H 4 / |
H
Ch
) ‘a C=..a
uN | LK |
(Ge ee es ee er fe
He | |
H ‘Sed?
Fig. 17.4 Mechanism of the reaction of ethene with chlorine

Polymerisation
Alkenes are the raw materials in the industrial manufacture of plastics. In
the polymerisation of ethene, the molecule adds to itself to produce a
saturated hydrocarbon chain that consists of repeating —CH,CH.— units.

The resulting solid substance is called poly(ethene) and has many uses, such
as in plastic bags and in food-wrapping films. Polythene is an example of a
polymer, a large molecule made up of many identical repeating units called
monomers. Physical properties, such as hardness, depend on the number of
carbon atoms in the polymer chain.
 ORGANIC CHEMICAL REACTIONS of

A polymer is a large molecule made up of many repeating

units called monomers.

If a different alkene is used, a similar reaction occurs, but the product will
have different atoms or groups bonded to the carbon chain. For example,
propene (CH,=CHCH,) polymerises to form poly(propene). This product
differs from polythene in that every second carbon in the chain has a methyl
group attached. Poly(propene) is used to make crates, stacking chairs and
ropes.

H CH, LH CH HCH, |
2 eo ee eee,
vA heat,

FA os catalyst | | |

H H L H H H H |

Polythene and poly(propene) are but two of a very large number of products
of the petrochemical industry. Other products include other plastics and
various dyes, pharmaceuticals, fabrics and solvents.

Substitution reactions: halogenation of alkanes

A substitution reaction is a reaction in which an atom or group of

atoms ina molecule is replaced by another atom or group of atoms.

In these reactions, one or more atoms of a halogen such as chlorine replace

hydrogen atoms in the alkane molecule. Ultraviolet light or high
temperatures are usually required for these reactions to take place. The
chlorination of methane is used to illustrate the reaction:

H H
| |
UV light |
Piece Sin Arch ca Gan) SEA HEl
| |
H H
. Chloromethane

Fig. 17.5 Chlorination of methane

Reaction mechanism: free radical substitution = pilesiteh3

Initiation
In the first step of the reaction, the ultraviolet light causes splitting of the
chlorine molecules into:two identical chlorine atoms. The chlorine atoms
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

are highly reactive, due to having an unpaired electron each. The dot on the
symbol indicates an unpaired electron.
Cinieee . 3
cl— Cl''+ UV — Cl+ Cl

Fig. 17.6 Initiation

Propagation
Each chlorine atom reacts with a methane molecule, removing a hydrogen
atom to form hydrogen chloride (HCl). This leaves the methyl free
radical, CH,”, which is highly reactive due to the presence of an unpaired
electron. It reacts immediately with a chlorine molecule, generating
another chlorine atom. This atom can react with another methane
molecule, so the two propagation steps can be repeated indefinitely in a
chain reaction.

LES
H:C—— Hv Cl> .—>- CH. + A)

alata
(laky aF cl —cl =e CHGl ae Glis

Fig. 17.7 Propagation

Termination
As the concentration of chlorine molecules drops, other reactions become
more likely, where two radicals combine in termination reactions. These are
bond-forming reactions, using up the reactive species.
iis
tEG ot i CH, srg H3C 7 ed GE

CN Fx
HC) su BCI er CH;Cl

Fig. 17.8 Termination “

There is considerable evidence for the free radical mechanism. When a

mixture of an alkane and chlorine is irradiated with ultraviolet light for
even a short period, a chain reaction occurs. The formation of ethane (or
butane in the chlorination of ethane) is evidence of the termination steps.
Further evidence is provided by the fact that these reactions are speeded up
by the addition of known sources of free radicals such as tetraethyllead.

Other substitution reactions

Esterification
Ester formation is an example of a substitution reaction. Focal
ethanoic acid (CH, ;COOH) reacts with ethanol (C,H 50H) to form ethyl
ethanoate (CH, CHOC, oid =) and water.
 ___ORGANIC CHEMICAL REACTIONS [7
H| 0 H H
VY ||
H— Cc — = + H C G O H_ heat, concentrated H,SO,
| | | '
H eheedy H H
Ethanoic acid Ethanol

H H H
a, on ‘
H e \S O \a f H + H,O
| oar
H H H
Ethyl ethanoate

Fig. 17.9

This is a reversible reaction, which proceeds very slowly in the absence of a

catalyst. It is catalysed by hydrogen ions (H*), which are supplied by
adding sulfuric acid. There is no change in structure, as the carboxyl carbon
atom remains planar.

Base hydrolysis of esters

Reactions of substances with water are called hydrolysis reactions. For
example, if an ester such as ethyl ethanoate reacts with water, the reverse of
ester formation occurs.

= im, 2
| C= GOH
ea HO
ene
ay Gen Pee aan
Nog | x |
HA H OH He A
Fig. 17.10 The reaction of ethyl ethanoate with water

A similar reaction occurs when a base such as sodium hydroxide reacts with
an ester. However, one of the products this time is the sodium salt of the
carboxylic acid.
H % H ms H oH
ay? KET, brady
iC ii i + NaOHe. ee ae tte tee Ge CO
H
; 10— 0 C= H H
fer PS. ONA a) sda
eis

Fig. 17.11 The reaction of ethyl ethanoate with sodium hydroxide solution

These are further examples of substitution reactions. There is no change in

structure, as the carbon atom in the ester linkage remains planar. It is called
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

a base hydrolysis of an ester, or a saponification reaction, and occurs in

soap making.

Soap
Soaps are the sodium or potassium salts of long-chain carboxylic acids. Soap
is generally made by the base hydrolysis of the esters present in vegetable
oils or animal fats.

Animal fats and vegetable oils are esters of long-chain carboxylic acids and
of the alcohol propane-1,2,3-triol (glycerol). The base hydrolysis of these
substances produces glycerol and the salt of the acid present, 1.e. soap. For
example, if the animal fat contains esters of stearic acid, the reaction is as
follows:
C,,H,,COO — CH, C,,H,,COOK = CH,OH
+ |
C,,H3,COO — CH + 3KOH > C,,H,,COOK + CHOH
| + |
C,,H;.<COO — CH, C,5HCOOK . CHjOH
. Potassium stearate Glycerol

Potassium:stearate is the soap formed in this particular case. The soap is a

long-chain hydrocarbon with an ionic group at the end. The non-polar part
dissolves grease, while the ionic end dissolves in water. This combination of
properties gives it its cleansing action.

Mandatory Experiment 17.1: Preparation of soap

Procedure: .
1 Add 3 cm? of vegetable oil, 2.5 g of potassium hydroxide and
20 cm? of ethanol, along with a few anti-bumping granules, to a flask.
Swirl to mix.
2 Assemble the apparatus for reflux (Fig. 17.12), greasing all joints in the
process.
3 Reflux the mixture for 20 minutes, using a water bath.
4 When cool, reassemble for distillation, Remove the ethanol by
distillation (Fig. 17.13).
Add about 15 cm? of hot water to dissolve the residue.
Pour this solution into a beaker of brine. The soap will precipitate out.
Filter the soap.
FONTest the soap for its lathering qualities by shaking a small sample of it
SOL
i
=

with water. It should form a lather readily.

 ee ORGANIC CHEMICAL REACTIONS.
Water out
—

Condenser
Water out
Water in
Condenser
Reflux reaction
products
Vegetable oil,
potassium hydroxide
and ethanol Water bath
Water bath Water in

Fig. 17.12 Fig. 17.13

Elimination reactions
Alcohols may be converted into alkenes in a dehydration reaction, which
involves the elimination of a molecule of water. The change in structure in
elimination reactions is from tetrahedral carbon to planar carbon, the
opposite of addition reactions.
H H H H
hei y
H CcC—cCc Oe ==. C=C + H,O

‘ales
H H H
Ethene

Fig. 17.14 Dehydration of ethanol

Mandatory Experiment 17.2: Preparation

and properties of ethene
Procedure HOSS
CEES SOOHOSHSEHOESERSOHSEHRESOTSOEOOEHHOSHOHOTHHEHEOHHOEHOHTHOTHEREOSEOESEHOSEHOOHHHHSHEBOTSEH

Preparation
1 Pour ethanol into a boiling tube to a depth of about 2 cm.
2 Push in enough glass wool to soak up all of the ethanol.
3 Set up the apparatus as shown in Figure 17.15, with about 2 g of
aluminium oxide heaped halfway along the boiling tube.
4 Heat the catalyst strongly, and occasionally heat the ethanol gently
to drive the vapour over the catalyst.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

5 Collect a few test tubes of ethene by displacement of water, stoppering

the test tubes when they are filled. The first test tube filled can be
discarded, as it contains a mixture of air and ethene.
6 When the reaction has concluded, remove the tube from the water, and
then turn off the Bunsen burner.

Glass wool Aluminium Ethene

andethanol oxide

Bunsen
burner

Water

Fig. 17.15

Investigation of properties
1 Ignite the ethene gas in one-of the test tubes. Record whether the flame
is coloured or clear, smoky or clean. Pour a few drops of limewater into
the test tube. Stopper and shake well. The limewater will be seen to
have turned milky.
2 Add a few drops of diluted bromine water to another test tube of ethene
gas. Stopper and shake well. The bromine water will have decolourised.
3 Add a few drops of acidified potassium manganate(VII) solution to a
third test tube of the ethene gas. Stopper and shake well. The
manganate(VII) solution will have decolourised.

Redox reactions
Oxidation of organic compounds may take place by the process of combustion
(burning) in oxygen, or by chemical reaction with other oxidising agents.

Combustion
Most organic compounds burn in air to form carbon dioxide and water. An
example is the combustion of ethanol:

C,H.OH\,) + 3054) > 2CO 4) + 3H,0W)

This reaction is exothermic, and ethanol is used as a fuel in countries where

it can be produced cheaply.

Alkanes with all of their hydrogen atoms replaced by halogen atoms are non-
flammable. The compound CBrCcirF.,, known as BCE, makes an effective fire
extinguisher, blanketing a fire in a dense non-flammable vapour that excludes
oxygen. Unfortunately, these compounds cause the same environmental
problems as CFCs (chlorofluorocarbons), which are responsible for damaging
 — ae _____ ORGANIC CHEMICAL REACTIONS <9 f 7
the ozone layer in the upper atmosphere. Consequently, they are being
replaced in fire extinguishers by carbon dioxide and other substances.

Beane: PUY oxtalsiny agents

Two oxidising agents commonly used for this purpose are potassium
manganate(VIJ), KMnO,, and sodium dichromate(V]), NajCr50_.

Potassium manganate(VII) is purple in colour and contains the MnO AON:

The oxidation number of manganese in this compound is +7. The oxidation
number changes to +4 (brown colour) or +2 (colourless), depending on the
extent of the reduction of the manganese.

Sodium dichromate(VI) is orange in colour and contains the Cr Ors ion.

The oxidation number of chromium in this compound is +6. The oxidation
number changes to +3 (dark green colour) when the chromium is reduced.

(i) Oxidation as alcohols to aldehydes

Primary alcohols undergo oxidation to aldehydes:

[O]
RCH,OH — RCHO

For example, ethanol (C,H,OH) is converted to ethanal (CH,CHO):

Ho. H H H
[73 | pense io ee
Hae Ola O29 C1207" tear Hg Hi C_26 +. H,O
Heat \&
| | | O
Hot H
Ethanal

In terms of structure, tetrahedral carbon has changed to planar carbon.

(ii) Oxidation of aldehydes to carboxylic acids
Ease of oxidation forming carboxylic acids is one of the most notable
characteristics of aldehydes.
[O]
RCHO — RCOOH
»

For example, ethanal (CH,CHO) is converted to ethanoic acid (CH,COORH):

H H i C
rt
|
120) C sds we
eenvcot VA
see a H Cre H G G + H,O

| \ ea
| ~S
4 O H OH
Ethanoic acid
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Since the planar carbonyl group, —C = O, is part of both the aldehyde and
carboxylic acid functional groups, there is no change in structure of the
affected carbon.

The ease of oxidation of aldehydes is illustrated by three different reactions

that can be used to identify the presence of the aldehyde functional group.
@ When an aldehyde reacts on heating with acidified potassium
manganate(VII) solution, the purple colour disappears. The aldehyde
is oxidised to a carboxylic acid. For example, ethanal is oxidised to
ethanoic acid:

CH;CHO > CH,COOH

Mnt? — Mn
purple colourless

@ Fehling’s reagent contains copper(II) ions, which are blue in colour.

On heating, aldehydes reduce the copper(II) ions to copper(I) ions,
and a brick-red precipitate of copper(I) oxide is formed:
Cuz + 6 >-cu
blue red

@ Ammoniacal silver nitrate, referred to as Tollens’ reagent, contains

silver(I) ions (Ag*). Aldehydes reduce the silver(I) ions on heating to
metallic silver (Ag).

Ag +E 6 => gy
colourless silver

If a very clean or new test-tube is used, the silver will be deposited on

its walls as a silver mirror.

If the three reactions above are attempted with a ketone such as propanone,
no colour changes are seen because the ketone is not capable of reducing
the reagents in question.

Mandatory Experiment 17.3: Preparation

and properties of ethanal
A primary alcohol can be oxidised to an aldehyde using sodium dichromate
solution, acidified with sulfuric acid. By using more alcohol than
oxidising agent, and by distilling off the ethanal as soon as it is
formed, further oxidation to ethanoic acid can be minimised. In this
experiment, ethanol is oxidised to ethanal:
Na,Cr,0./H,SO,
C,H.OH > CH,CHO
The balanced equation for the reaction is:
3C,H,OH + Cr,0,2 + 8H* —» 3CH,CHO + 2Cr3+ + 7H,O
Procedure
(i) Preparation
1 Set up the apparatus for distillation with addition, as shown in
Figure 17.16.
2 Place 12 cm? of water in the reaction flask and add some anti-bumping
granules.
3 Slowly, with swirling and cooling under a cold-water tap, add 4 cm? of
concentrated sulfuric acid.
4 Dissolve 10 g of sodium dichromate in 10 cm? of water in a clean small
beaker, and then add 10 cm? of ethanol. Place this solution in the
dropping funnel, using a small plastic funnel.
5 Arrange the conical collection flask so that it is standing in a large
beaker of ice/water. Ethanal is volatile, and the cold conditions will
minimise loss by evaporation.
6 Heat the dilute acid gently until it just boils, and then remove the heat
source. Further heating is not required as the reaction is exothermic.
7 Slowly add the alcohol/dichromate mixture from the dropping funnel so as
to maintain a gentle boiling. The ethanal distils off as it is formed.
8 Redistill the impure ethanal and collect the fraction boiling between
20°C and-2>°C.

Dropping funnel containing

sodium dichromate,
water and ethanol

Water out

Flask containing water,

concentrated H,SO, and
anti-bumping granules
Conical flask
Ice/water mixture

Fig. 17.16 211)

 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

(ii) Properties
Oxidation by acidified potassium manganate(VIl) solution
1 Add 1 cm? of potassium manganate(VII) solution and 4 cm? of dilute
sulfuric acid to about 2 cm? of ethanal in a test tube.
2 Warm the test tube in a water bath and shake gently. The
manganate(VII) solution decolourises.

Oxidation by Fehling’s solution

1 Mix about 1 cm? each of Fehling’s solution No. 1 and Fehling’s solution
No. 2 in a test tube.
2 Swirl the contents so that the blue precipitate initially formed will dissolve.
3 Add 1 cm? of ethanal, heat gently and shake.
4 A brick-red precipitate is formed.

Silver mirror test (oxidation by ammoniacal silver nitrate)

1 Place 3 cm? of silver nitrate solution and 1 cm? of sodium hydroxide
solution in a clean test tube.
2 Add aqueous ammonia solution dropwise, with shaking, until the
precipitate formed in step 1 is just dissolved.
3 Add two or three drops of ethanal, shake and warm in a water bath.
4 A silver mirror forms on the inside wall of the test tube.

Ethanal is formed in the human body when ethanol from alcoholic drink is
metabolised. Since the change is from alcohol to aldehyde, the process
involves oxidation. The ethanal formed in the body is a cause of some of the
unpleasant effects of an alcohol-induced hangover.

(iii) Oxidation of alcohols to carboxylic acids

Mandatory Experiment 17.4: Preparation

and properties of ethanoic acid
A primary alcohol can be oxidised to a carboxylic acid by refluxing with
sodium dichromate solution, acidified with sulfuric acid. During refluxing,
any ethanal or ethanol vapour that leaves the reaction mixture condenses and
falls back into the reaction flask for further oxidation. By using more
oxidising agent than alcohol, and by refluxing the reaction mixture for
20 to 30 minutes, any aldehyde formed is oxidised to carboxylic acid.
In this experiment, ethanol is oxidised to ethanoic acid:
rey

Na,Cr,0,/H,SO,
C,H.OH — CH,COOH
The balanced equation for the reaction is:
(12) 3C,H.OH + 2Cr,0,?> + 16H* — 3CH,COOH + 4Cr3+ + 11H,O
 __ ORGANIC CHEMICAL REACTIONS
Procedure

(i) Preparation
1 Place 10 cm? of dilute sulfuric acid in the reaction flask, and add some
anti-bumping granules.
2 Add in 9 g of sodium dichromate and dissolve in the acid by careful
swirling.
3 Add 6 cm? of concentrated sulfuric acid slowly, with swirling and
cooling, in an ice bath. Set up the apparatus for reflux with addition, as
shown in Fig. 17.17.
4 Mix 2 cm? of ethanol and 10 cm? of deionised water, and place in the
dropping funnel.
5 Very slowly add the solution from the dropping funnel down the
condenser, while swirling and cooling the contents of the flask.
6 Remove the dropping funnel and still head from the top of the
assembled apparatus.
7 Using a water bath, boil the mixture gently for about half an hour.
8 When the apparatus is cool enough to handle safely, dismantle and
rearrange for distillation. Direct heating without a water bath
must be used, as the boiling point of the mixture will eventually exceed
100°C.
9 Distil off about 15 cm». This is aqueous ethanoic acid.

Water in

Sodium dichromate solution

and sulfuric acid
and anti-bumping granules

Fig. 17.17 (213)

LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

(ii) Properties
1 Odour: Ethanoic acid has a sharp, vinegar-like smell (vinegar is a dilute
solution of ethanoic acid).
2 Test with universal indicator paper: Dip some universal indicator
paper in the distillate and note that the pH is less than 7.
3. Test with magnesium: Drop a 5 cm clean strip of magnesium into
some distillate in a test tube and swirl. Bubbles of hydrogen gas will be
given off, which will burn with a pop.
4 Test with sodium carbonate: Add 1 g of anhydrous sodium carbonate
powder to some distillate in a test tube and swirl. Bubbles of carbon
dioxide will be produced.
5 Esterification: Carefully add 2 drops of concentrated sulfuric acid to
some distillate in a test tube. Add 1 cm? of ethanol and warm gently.
An oily layer with a sweet smell will be produced.

Reduction ofcarbonyl compounds

The cecon of primary alcohols to aldehydecstecan be reversed ba Malye
hydrogenation, using hydrogen passed over the surface of a heated catalyst
such as nickel. For example, ethanal is reduced to ethanol:

. en
H H H H

aA== C=
anes € + H, Sdn: ‘E G OH
| \ eal
H O H H
Ethanal Ethanol

Reactions as acids
Some organic compounds can act as acids, losing a proton in certain
situations. The hydroxyl hydrogen is involved, not the carbon~chain, so
there is no change in structure. Organic acids are weak acids, with small
K_ values, and do not have a strong tendency to donate a proton.

Acidic properties ofalcohols

SSHOSSSHSHSTHTTHESHS HOSS HSHOSSSS
MRSS Sse sEesenseseoeeeosEesn

NESE are eremeys seal are with very little tendency to donate cre
Forcing conditions are necessary to enable them to do so. Alcohols will react
with very active metals such as sodium. For example, ethanol will react with
sodium, releasing hydrogen gas and forming a salt, sodium ethoxide:
HH HH
ea ae
H— C— C Oe HiasiNe > H— C— C —ONa’ + FH,
Nm ary
HH HH
Sodium ethoxide
 _ ; i: _____ ORGANIC CHEMICAL REACTIONS

Reactionsof
carboxylic acids
Echencie. Seidl (CH,COOH) is arae prongs facil chan Mehamel: Bsout
5 x 10! times stronger.

The more reactive an acid is, the more stable its anion or conjugate
base. When ethanoic acid loses a proton, its conjugate base, the
ethanoate ion (CH,COO), is formed. Two structures are possible for
this ion.

H O H oO
L A eZ
5 ar Ora, AH. GG
ewe roe Ss
H O H
Fig. 17.18

Each has a carbon—oxygen single and a carbon—oxygen double bond.

However, the actual carbon—oxygen bond lengths in the ion are equal,
suggesting that the structure is in between the two structures shown.
The effect is that the negative charge on the ion is spread out over three
atoms, the carbon and both of the oxygens. This spreading out or
delocalisation of charge is a stable arrangement, making the ion less
reactive, and this is consistent with the acid itself being relatively
reactive.

(i) Reaction with magnesium metal

CRSSCHSCSHETHEESHEHSHESHESEESHESESESEHEHEEEEED

Carboxylic acids react with magnesium eis Voeere afait ace Pelee ne
hydrogen gas.

H O H o \
| We | Vj,
2h GG Mg ——— | H—.C—C Mg + H,
| |
H OH H O

SSOHHOEHHHHEHEHOHEHTSHHOSEHEHSSESHSESHSHHEHEHTHETHE
SS HHOHEHE OSS
RSH HOHEESESHESEH
CORO OS SOEHESES

Carboxylic acids react with alkalis, fonts a salt and water.

H H
O | O
| ZL Wz
He C==C .4.Na0h eC Ce ae tO
4| \ OH H
| SS ONa
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

(iii) Reaction with sodium carbonate SCRESCHRSSHORESEHOESHESCHESHTEGTEREHRETBOE

Garboxylic ans react eich Sarbornites onan a ~ salt, water and

releasing carbon dioxide gas.

H H
O
| ee | Vi
2G — & + Na,CO; ny ee +h COm te Le
oN |
| OH H ONa

Organic synthesis
Synthesis is the formation of chemical compounds from simpler
compounds. For example, salicylic acid — aspirin — is available from the
bark of the willow tree, but is usually synthesised in the laboratory. Organic
synthesis involves bond breaking and bond making.

The synthesis of PVC from ethene

The first step is the chlorination of ethene to form 1,2-dichloroethane:

CH=CH, + Cl, > CH,CI-CH,Cl

The 1,2-dichloroethane is vaporised and heated to form chloroethene
and hydrogen chloride:
CH,CI-CH,Cl > CH,=CHCI + HCI
The chloroethene is polymerised by heating in the presence of a
catalyst at high pressure. The product poly(chloroethene) is usually
referred to as PVC. Two repeating units are shown:

(i 0c
GC
eal
SPW
< 5
 ae = > Pee ys ait _ ORGANIC CHEMICAL REACTIONS =

Example 17.1
Outline the synthesis of ethane from ethanal.

Answer
The first step is the reduction of ethanal to ethanol by catalytic hydrogenation:

CH,CHO + H, > C,H.OH

The ethanol is then dehydrated to ethene, by passing its vapour over a hot
aluminium oxide catalyst:

CSH-OR-> CH;

Ethane is formed by the catalytic hydrogenation of ethene:

rah +H, CoH,

Ethane

An addition reaction is a reaction in which two molecules add

together to form one larger molecule.
A reaction mechanism is a detailed step-by-step account of how an overall
reaction Occurs.
A polymer is a, large molecule made up of many repeating units called
monomers.
A substitution reaction is a reaction in which an atom or group of atoms
in a molecule is replaced by another atom or group of atoms.

Your revision notes

 CHAPTER 18
Chromatography and
instrumentation in Organic Chemistr

@®® Topics Covered in this Chapter

Chromatography
Paper chromatography
Thin layer chromatography
Column chromatography
Gas chromatography (GC)
High-performance liquid chromatography (HPLC)
Mass spectrometry
Ultraviolet absorption spectrometry
Infrared absorption spectrometry

Introduction to chromatography

Chromatography is a type of separation technique that

involves the use of a mobile phase and a stationary phase to
separate the components of a mixture from each other.

Table 18.1 Simple chromatography methods

“Method ==—~—_ Stationary phase Mobile phase

Paper chromatography = Water on paper Liquid
Thin layer chromatography Solid Liquid
Column chromatography Solid Liquid

Paper chromatography
Chromatography paper contains adsorbed water. When the chromatogram
is being run, the solvent moves through the adsorbed water. Substances that
are more soluble in the moving solvent tend to be carried on, while
substances that are more soluble in water are held back.
 _ CHROMATOGRAPHY AND INSTRUMENTATION IN ORGANIC CHEMISTRY

Maktatiie eerhicue 18.1: Separation of a

mixture of indicators using paper chromatography
Procedure
SHHHOSHELETHOHHHLHESHHETESHAESSESSSEHROSHEHEEHHAEKE

1 Add he Sie to The benronn af the i

tank to a depth of about 10 mm.
Cover the tank and allow to stand for a
few hours. This will allow the tank to Tepk
become saturated with solvent vapour. _
2 Make a line with a pencil about 3 cm St
from the bottom of a rectangular See
sheet of chromatography paper and
another line near the top.
Fig. 18.1
3 Using a capillary tube, place a small
spot of each indicator and of the mixture of indicators at different points
on the line near the bottom of the paper. Dry using a hair drier and repeat.
4 Place the chromatogram in the tank, taking care that the solvent level in
the tank is below the line on which the indicator samples are spotted.
5 Run the chromatogram until the solvent reaches the line near the top of
the paper.
6 Remove and dry.
7 Identify the indicators present in the mixture.

Thin layer chromatography

For thin layer chromatography (Fig. 18.2), thin layer chromatography plates
and a glass tank are needed. The thin layer chromatography tank contains a
suitable solvent and should be saturated with solvent vapour before use.

Tank

Thin layer plate

>

Solvent

Fig. 18.2

Uses of thin layer chromatography

SHRASHSHSHOHSHATC HSS SSSOHRFEHSSESSHSFSTSHOOHSEAHSHRHEHSSOHHHSHESOHOETHHAIHHEHSE?Y

Thin layer chromatography iis particularly dcerulisin nena aa ivecan“be

used for example to separate dyes taken from fabrics at the scene of a crime.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Column chromatography
In column chromatography, a small amount of the mixture to be separated
is placed on a suitable column, and a suitable solvent is used to carry the
mixture through the column. A particularly useful type of column is a solid
phase extraction column (Fig. 18.3).

Solid phase extraction column

Stationary phase

Fig. 18.3 Solid phase extraction column

Solid phase extraction columns can be used to separate the components of a

mixture of indicators.

Gas chromatography (GC)

A gas chromatograph is an instrument particularly suited to separating the
components of a volatile mixture. In gas chromatography, the mobile phase
is a gas and the stationary phase is a non-volatile liquid (which is coated on
fine particles of an inert solid).

A sample of the mixture to be separated is injected into the instrument and

is carried through the column by the flow of gas. The components are
separated and detected.

The separation is based on the fact that more volatile components of the
mixture tend to be swept along faster by the gas than less volatile
components, and also that different components are attracted to different
extents by the non-volatile liquid in the column.

Table 18.2 Gas chromatography

Different components of a mixture @ Injection

have different interactions with the @ Transport of the sample
stationary and mobile phases along the column
@ Separation in the column
@ Detection

In analytical work, a gas chromatograph is sometimes used in conjunction

with a mass spectrometer. The gas chromatograph separates the different
 CHROMATOGRAPHY AND INSTRUMENTATION IN ORGANIC CHEMISTRY fy

components of the mixture being analysed, and each component is then

separately analysed by the mass spectrometer.

Uses of gas chromatography

Ties: include drug tests on athletes and blood alcohol tests.

High-performance liquid chromatography (HPCC)

A high-performance liquid chromatograph is an instrument particularly
suited to separating the components of a non-volatile mixture. In high-
performance liquid chromatography, the mobile phase is a solvent and the
stationary phase consists of very fine particles of silica.

High pressure has to be applied to the solvent to force it through the

column. A sample of the mixture to be separated is injected into the
instrument and is carried through the column by the solvent. The
components are separated and detected.

The separation is based on the different tendencies of the different

components of the mixture to be adsorbed onto the silica in the column.

Table 18.3 High-performance liquid chromatography (HPLC)

_ Different components of a mixture @ Injection

have different tendencies to adsorb e@ Transport of the ane a
onto very fine particles of a solid in along the column
the HPLC column @ Separation in the column
@ Detection —

Uses of high- performance liquid chromatography

ree include analysis of growth promoters in meat and of vitamins in1 foods.

Mass spectrometry
Table 18.4 Mass spectrometry

Posi charged ions are separated — ® \aporisation

ont sis of their relative masses @ = lonisation —
in a magnetic tield — @ Acceleration
ty ee - @ Separation
e Detection — Gai)
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Mass spectrometry can be used to measure the relative atomic mass of an

element and to measure the relative molecular mass of a substance. A
further use of mass spectrometry in organic chemistry is in the
identification of substances.

In a mass spectrometer, molecules are ionised and broken into positively

charged fragments with different masses. These are separated and the
relative amounts recorded, giving the mass spectrum of the molecule.
Different molecules have different mass spectra. The mass spectrum can be
used to identify the substance.

Uses ofmass spectrometry

iWeKe spectrometry is used to analyse gases from a waste quae It is aise
used to analyse organic pollutants in water.

Ultraviolet absorption spectrometry (UV)

Ultraviolet absorption spectrometry is a technique involving the absorption
of ultraviolet radiation. It is a quantitative technique, that is, it can be used
to measure the amount of a substance in a sample.

In ultraviolet absorption spectrometry, a solution of the substance under

investigation is placed between a source of ultraviolet light and a detector.
The detector analyses the intensity of the light that reaches the detector
relative to the intensity of the light passing into the solution. In this way,
an absorption spectrum is obtained.

Table 18.5 Ultraviolet absorption spectrometry

Fr ie ys "Processes
Absorption of ultraviolet radiation by e Ultraviolet ma is passed
molecules results in the promotion of through the sample and
electrons from their ground state energy a blank
levels to higher energy states. Absorbance is @ An absorption spectrum
directly proportional to concentration is obtained

Uses of ultraviolet absorption spectrometry

Ulecaviolés abortion spectrometry is used in sche vanalyae vatevlna
metabolites and of plant pigments.

(nfrared absorption spectrometry (IR)

Infrared absorption spectrometry is a technique involving the absorption of
e) infrared radiation. It is a particularly useful technique for identifying
 CHROMATOGRAPHY AND INSTRUMENTATION IN ORGANIC CHEMISTRY
organic compounds, as each compound has its own almost unique infrared
spectrum.

In infrared absorption spectrometry, a sample of the substance under

investigation is placed between a source of infrared light and a detector. The
detector analyses the intensity of the light that reaches the detector relative
to the intensity of the light going into the sample. In this way, an
absorption spectrum is obtained.

Table 18.6 Infrared absorption spectrometry

Principle _ _ Processes ;
Molecules of a substance absorb ® Infrared radiation passes Tes
infrared light of different frequencies. the sample
The combination of frequencies e@ The sample absorbs infrared
absorbed is peculiar to the molecules radiation at specific wavelengths
of that substance which are detected
e An absorption spectrum is
obtained

Uses ofinfraredRE Peo

Chromatography is a type of separation technique that involves the

use of a mobile phase and a stationary phase to separate the components
- of a mixture from each other.
There are three simple methods of chromatography: paper, thin layer, and
column chromatography.
The principle underlying gas chromatography is that different components
of a mixture have different interactions with the stationary and mobile
phases.
The processes involved in gas chromatography are: (1) injection,
(2) transport of the sample along the column, (3) separation in the column,
and (4) detection.
The principle underlying high-performance liquid chromatography (HPLC) is
that different components of a mixture have different tendencies to adsorb
onto very fine particles of a solid in the HPLC column.

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The processes involved in high-performance liquid chromatography are: (1)

injection, (2) transport of the sample along the column, (3) separation in
the column, and (4) detection.
The principle underlying mass spectrometry is that positively charged ions
are separated on the basis of their relative masses in a magnetic field.
The five fundamental processes involved in mass spectrometry are:
(1) vaporisation, (2) ionisation, (3) acceleration, (4) separation and
(5) detection.
The principle underlying ultraviolet absorption spectrometry is that the
absorption of ultraviolet radiation by molecules results in the promotion of
electrons from their ground state energy levels to higher energy states.
Absorbance is directly proportional to concentration.
The processes involved in ultraviolet absorption spectrometry are:
(1) ultraviolet light is passed through the sample and a blank, and
(2) an absorption spectrum is obtained.
The principle underlying infrared absorption spectrometry is that molecules
of a substance absorb infrared light of different frequencies. The
combination of frequencies absorbed is peculiar to the molecules of that
substance.
The. processes involved in infrared absorption spectrometry are:
(1) infrared radiation passes through the sample, (2) the sample absorbs
infrared radiation at specific wavelengths which are detected, and (3) an
absorption spectrum is obtained.

Your revision notes

 CHAPTER 19
Chemical Equilibrium

@ © Topics Covered in this Chapter

Reversible reactions
Dynamic equilibrium and chemical equilibrium
Equilibrium constants
Calculations of equilibrium constant values
Calculations of equilibrium concentrations
Le Chatelier’s principle
Industrial applications of Le Chatelier’s principle

Reversible reactions
Ammonia is manufactured by reacting nitrogen with hydrogen:

N, + 3H, = 2NH,
—

The symbol = indicates that the reaction is reversible. The conversion of

reactants to products is never complete no matter how long the reaction is
allowed to continue.

A reversible reaction is a reaction that can take

place in either direction.

Dynamic equilibrium and chemical equilibrium

In a mixture of nitrogen gas and hydrogen gas in a closed container at
700 K, nitrogen molecules and hydrogen molecules only are present
initially. As they react, forming ammonia molecules, the concentrations
of both nitrogen and hydrogen decrease, while the concentration of
ammonia increases. Eventually, however, they level off and become
constant.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

- H, +—Equilibrium concentration of hydrogen

|
eral age . ° .
NH+— Equilibrium concentration of ammonia
Concentration
—>
zant = Nt Equilibrium concentration of nitrogen
|

Time —>

Fig. 19.1 Concentrations of nitrogen, hydrogen and ammonia

level off to equilibrium values

When the concentrations of reactants (N, and aby, and product (NH,)
have become constant, a state of chemical equilibrium is said to have
been reached.

At equilibrium, the rate of the forward reaction equals the rate of the
reverse reaction.

_ Chemical equilibrium is said to be dynamic because, at

~ equilibrium, there are reactions continually occurring, and the rate
of the forward reaction equals the rate of the reverse reaction.

Equilibrium constants
In the reaction

Hye = el
as much hydrogen iodide is decomposing at equilibrium as is being formed,
and so the concentrations of all three substances remain constant. There is
a constant relationship that holds here, namely :

cD aee
eIxIb] = constant

where the square brackets denote concentrations in mol I-!. In general, if m

moles ofA react with n moles of B forming p moles of C and q moles of D:
mA +nB = pC + qD

ig
[A]™ [By] ae

where Kis a constant, called the equilibrium constant in terms of molar

concentration. This relationship is known as the equilibrium law.
 CHEMICAL EQUILIBRIUM
The value of the equilibrium constant depends on the temperature. If the
forward reaction is exothermic, the equilibrium constant decreases as the
temperature rises; if it is endothermic, it increases.

Example 19.1
Write an expression for the equilibrium constant (K.) for the following
reversible reaction:
2NO +0, = 2NO,
Answer

_ _[NO2/
S
[NO}* [05] —

Important points about equilibrium constants

@ The value of K_ only applies at equilibrium.
@ K is constant only if the temperature remains constant.
@ The value of K, is not affected by changes in concentrations of
reactants or products.
@ The units of K, depend on the relative numbers of moles on each
side of the equation for the reaction. In a reaction in which there
are equal numbers of moles on each side of the equation, such as
H, +l, = 2HI
K_has no units, as all units cancel in the K, expression. Otherwise,
K_ has units. For example, the unit of K, for the reaction
NO +0, =2N0,
is mol! 1.

Calculations of equilibrium constant values

If the equilibrium concentrations of all species in a given reaction are
known, as in Example 19.2, the equilibrium constant value may readily be
calculated.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 19.2
In a reaction at a particular temperature between nitrogen and hydrogen
forming ammonia
N, + 3H, = 2NH;
it was found that at equilibrium the concentrations of N,, H, and NH, were
0.06 mol I-', 0.07 mol =! and 0.02 mol I, respectively. Calculate the value of
the equilibrium constant (K.) for this reaction at this temperature.

Answer

Cc
gE2 2a
2 .
ead mone le
[NjI[H>P — (0.06)(0.07)

To find the equilibrium constant for a reaction, it is usually necessary to

calculate the equilibrium concentrations of all the species first.

Example 19.3 |
Four moles of COCI, are placed in a 4-litre flask at 668 K. The following
reaction occurs: :
COG = CO. Gh
and, at equilibrium, 1.6 moles of COCI, remain. Calculate K_ for the reaction.

Answer
The equation for the reaction is:
\

COG = COgGl,

eee”
Initial amount 4 moles oe O moles ) moles ”
Change —(4- 1.6) moles +4-1.6 moles +4 - 1.6 moles
Equilibrium amount 1.6 moles 2.4 moles 2.4 moles
Equilibrium 1.6/4=0.4 2.4/4=0.6 2.4/4=0.6
concentration mol |"! mol ~ mol 1

_ (CONCh] _ 06x 0.6 =0.9 mol!

See [COCh] 0.4

In reversible reactions where neither the forward nor the reverse reactions
causes a change in the number of molecules present, it is possible to
calculate the equilibrium constant even if the volume of the equilibrium
mixture is unknown, using the method shown in Example 19.4.
——— i EP CHEMICAD EQUILIBRIUM
Example 19.4
In the reaction

C,HjCOOH + C,H.OH = C,H,COOC,H,. + HO

at 473 K, it is found that if an initial mixture containing 2 moles of C,H,COOH
and 2 moles of C,H.OH is allowed to come to equilibrium, 1 mole of
C,H,COOH remains. Calculate the equilibrium constant for the reaction at
473 K.

Answer
The equation for the reaction is:

C4HgCOOH + C,H,OH = C,HjCOOC,H, + H,0

iysoe w
| GHgCOOH HOH
tio ten
|
GyHjCOOC,H,
Initial amount -2 moles 2 moles 0 moles 0 moles
Change 2-—1moles 2-—1moles +1 mole +1 mole
Equilibrium 1mole 1 mole 1 mole 1 mole
amount
Equilibrium, = 1/Vmolh! 1/Vmoll 1/V mol br! 1/V mol F
concentration

Since the V values cancel,

[C4HoCOOC Hg] [H,0] _ (1/V)(1/V)

Ke= [C4HgCOOH] [C>HOH] (17 V)(17V) :

Calculations of equilibrium concentrations

In examples of this type, a quadratic equation in terms of x will usually be
arrived at during the calculation. For a quadratic equation ax* + bx + c= 0,
the value of x is found using the formula:

=> 4q)(b-—Aac)
. a 2a

Two different values of x will usually be obtained, one of which (often either
a negative value or a value which is too large to be possible) will have to be
rejected.
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 19.5
At 760 K, the value of K. for the reaction

PCIe = Pelee Cla

is 33 mol I-’. Calculate the equilibrium concentrations of all species if 10 moles
of PCI, are placed in a 1-litre flask at 760 K and allowed to reach equilibrium.

Answer
The balanced equation for the reaction is:

PCl ese PClne El)

The following table summarises the steps taken so far in the calculation:

7 PCIe PCI, ci,

Initial amount 10 moles O moles 0 moles

Change — x moles + x moles + x moles
Equilibrium amount 10-—x moles x moles x moles
Equilibrium concentration (10-x)/1 Kei xf1
(mol |-')

= =the [PCl3] x [Clo]

Ke a33moll = e TipC een

5
33 mol | Sct"
pet. PClg] x [Cl] molt? _ (x) x (x) mol177
ee, or Seer

{Xe = S910 = 50
=350=. 33%
x24 33x -— 330=0 *

Using the formula x =(—b

+ [b* — 4ac])/2a, we obtain:
x I (S 33+ y[1089+1320])/2
I] (—33 + [2409]) / 2
=(=33+ 49.081565)/2 .
1 6.081565 / 2 or —82.081565/2
= 8.04 or — 41.04

The negative value of x can be disregarded.

Concentrations at equilibrium:
[PCle] [PCI,] [Cl]
10-x/1molesl' x/1 moles I! x/1 moles |!
= 1.96 moles |! = 8.04 moles |"! = 8.04 moles |-'

230
 CHEMICAL EQUILIBRIUM
In reversible reactions where neither the forward nor the reverse reactions
causes a change in the number of moles present, it is possible to calculate
the equilibrium amounts of all species, even if the volume is unknown,
using the method shown in Example 19.6.

Example 19.6
Ethanoic acid reacts with propan-1-ol at 373 K, according to the equation:

CH3;COOH + C,H,OH = CH,COOC.H, + H,O

If the equilibrium constant for the reaction at this temperature is 6.25,

calculate the equilibrium amounts in moles of all species when 210 g of
CH3COOH and 210 g of C,H,OH are placed in a flask at 373 K.

Answer

210 g CH,;COOH = 210/ 60 = 3.5 moles

210 g C3H,OH = 210/60 = 3.5 moles

Let V litres be the total volume of the mixture at equilibrium. Assume that
x moles of propyl ethanoate and water, respectively, are formed at equilibrium.

PEHICOOH! ROH. CHCOOCH, © “HAO|

Initial amount 3.5 moles 3.5 moles O moles 0 moles
Change —xmoles —xmoles +x +X moles
Equilibrium 3.5-x 3.5-x + X + x moles
amount moles moles
Equilibrium (3.5-x)/V (3.5-x)/V x/V KEW.
concentration
(moles |-')

[CH3COOC3H,] [HO] (x/V)(x/V) 5655

OR [CH3COOH] [CH3H,OH] — ((3.5—x)/V) (3.5—x)/V)

From this is got the following quadratic equation:

5.25x* — 43.75x + 76.5625 = 0
»

Using the formula x =(—b+ [b* — 4ac])/2a, we obtain:

x = (443.754 J[1914.0625 —1607.8125])/10.5

= (+43.75+,/[306.25]) /10.5
=(443. 75447 5)/10:5
= 26.25/10.5 0r+61.25/10.5
=72,.5 or 5.83333

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Since x is the number of moles of propyl ethanoate or water formed,

x = 5.8333 is impossible, because the initial amounts (3.5 moles each) of ethanoic
acid and propanol are not capable of producing 5.83333 moles of propy!
ethanoate and water, respectively.

Amounts at equilibrium:
CH,COOH C,H,OH!. * CH;COOCAS "HO
1 mole 1 mole 2.5 moles. 2.5 moles

be Chatelier’s principle
Le Chatelier’s principle: When a system at equilibrium is subjected to a stress,
the equilibrium shifts in such a way as to minimise the effect of the stress.

4
®
*
6
&
*
a
*

Henri Louis
Le Chatelier

Table 19.1 summarises the changes at equilibrium predicted by Le Chatelier’s

principle (X refers to one of the components of the equilibrium mixture).

Table 19.1

2 é esultant change
Increase in concentration of X Reaction that removes_X is favoured
Decrease in concentration of X Reaction that forms X is favoured

Increase in temperature Endothermic reaction is favoured

Decrease in temperature Exothermic reaction is favoured
Increase in pressure Reaction that produces less molecules
is favoured
Decrease in pressure Reaction that produces more
molecules is favoured
Adding a catalyst No change
 CHEMICAL EQUILIBRIUM |

Example 19.7
In the reversible reaction

dec = 2HC
in which the forward reaction is exothermic, what is the effect at equilibrium of
(i) lowering the temperature
(ii) lowering the pressure
(iil) making the reaction container smaller
(iv) decreasing the amount of catalyst
) decreasing the amount of HCI
(vi) decreasing the amount of H,
i)y decreasing the amount of Cl,?

Answers
(i) Lowering the temperature: This favours the exothermic reaction,
forming hydrogen chloride.
(il) Lowering the. pressure: This has no effect, since there is the same
number of molecules on the left-hand side of the equation as on the
right-hand side.
(ili) Making the reaction container smaller: This has no effect, since there
is the same number of molecules on the left-hand side of the equation
as on the right-hand side.
(iv) Decreasing the amount of catalyst: This has no effect, since the
reaction mixture is already at equilibrium. (Using a catalyst lessens the
time needed ‘to reach equilibrium, if equilibrium has not been reached
already.)
(v) Decreasing the amount of HCI: This favours the reaction forming
hydrogen chloride.
(vi) Decreasing the amount of H,: This favours the reaction forming
hydrogen and chlorine.
(vii) Decreasing the amount of Cl,: This favours the reaction forming
hydrogen and chlorine.

Mandatory Experiment 19.1: Simple experiments

to illustrate be Chatelier’s principle
(a) Theequilibrium between CoCl,?" and Co(H,0),?*
When esbale chloride is Aittotreds in water, the focapound dissociates into
its ions, Cl- and Co**, and then Co(H,O),** — which is pink in aqueous
solution — is formed. A reversible reaction then occurs, in which water and
CoCL, — which is blue — are formed.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The following equilibrium is established:

CoCl,2- + 6H,0 = Co(H,0),** + 4Ch
blue pink

The forward reaction is exothermic.

Procedure
(i) Preparing the solution for the experiment
1 Dissolve 4 g of cobalt chloride-6-water in 40 cm? of deionised water. A
pink solution should be formed, indicating that the equilibrium lies on
the right-hand side. Keep a 2 cm? sample of this solution in a test tube
for reference.
In a fume cupboard, add concentrated hydrochloric acid, with stirring,
until a violet solution is formed. Keep a 2 cm? sample of this solution
in another test tube for reference.
Add more concentrated hydrochloric acid — this will produce a blue
colour, while adding water will restore the pink colour. By trial and
error produce an ‘in between’ violet (or lilac) colour which will contain
the two cobalt ions.
Place the violet solution in each of six boiling tubes to a depth of
about 2 cm.
(ii) To study the effects of concentration changes on the equilibrium
1 Keep one boiling tube as a control.
2 Add water to a second tube using a dropping pipette. The colour of the
solution should change to pink. This happens because the equilibrium
shifts to the right.
In a fume cupboard, add concentrated hydrochloric acid to a third tube using
a dropping pipette. The colour of the solution should change to blue. This
happens because the equilibrium shifts to the left.
(iii) To study the effects of temperature changes on the equilibrium 3
i Keep one boiling tube as a control. ‘
2 Place another tube in a beaker of hot water (over 90°C). Note that the colour
changes to blue. This happens because the equilibrium shifts to the left.
Place another tube in a beaker of crushed ice and water. Note that the
colour changes to pink. This happens because the equilibrium shifts to
the right.

(b) The equilibrium between Cr,0,?" and Cr0,?

A solution containing Phrometeul) ions reacts as Hollows inean anes
of acid:

2CrO, + 2H? = Cr,0,2> + HO

yellow orange
 —
CHEMICAL= EQUILIBRIUM
eee Ba ee —_ ee eee

Procedure
1 Quarter fill a boiling tube with the solution of sodium dichromate
provided. This should have an orange colour. Keep a second sample
of the sodium dichromate solution in a test tube as a control.
2 Carefully add some dilute sodium hydroxide solution until the
orange colour changes to yellow. This happens because the equilibrium
shifts to the right.
3 Carefully add dilute sulfuric acid until the yellow colour changes back
to orange. This happens because the equilibrium shifts to the left.

(c)Theequilibrium between Fe>* and Fe(CNS}?*

A Sjiittton of iron(II) chloride reacts with a solution a dWbacinee ions as
follows:
Fes+ + CNS~ = Fe(CNS)4+
yellow red

Adding hydrochloric acid reduces the concentration of Fe** by forming a

complex ion containing iron and chlorine. This causes a shift of equilibrium
to the left. The equilibrium can be shifted to the right-hand side by adding
some potassium thiocyanate solution.
Procedure
1 Mix together about 5 cm’, respectively, of solutions of iron(IID chloride
and potassium thiocyanate in a beaker. Note the formation
of the red complex. Divide the mixture into three portions in separate
boiling tubes. Keep one of these as a control.
2 Using a fume cupboard, add some concentrated hydrochloric acid to the
second tube until the red colour disappears. This happens because the
‘equilibrium shifts to the left.
3 Add an equivalent amount of water to the third tube and compare. This
comparison should indicate that the extent of lightening the colour is
not due to a diluting effect.
4 To the second tube, add some potassium thiocyanate solution. The
mixture goes red. This happens because the equilibrium shifts to the
right.

Industrial applications of be Chatelier’s principle

(i) Application of le Chatelier’s principle to the industrial
synthesis of ammonia HER OEHHA THHOHH OTH OTESIO
ESHRHEKSEHTHHHRSHHAHOHEHRESHSHHEHHAHHAHHSH ESE
PSC OSESESHSHOSHESERASASH

The synthesis of ammonia from its elements

N, + 3H, = 2NH, AH=-92 kJ mol"!
a) Ge Be LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

is an important process in the fertiliser industry. The process used to make

ammonia is called the Haber process.

In the industrial synthesis of ammonia, the objective is

to produce the maximum possible amount of ammonia
at the lowest cost and in the shortest possible time.
A balance has to be struck between factors that favour
a reasonable rate of reaction and those that favour a
reasonable yield.

Fritz Haber

1 Temperature

N, + 3H, = 2NH, _AH =-92 KJ mot!

Since the forward reaction is exothermic, it is favoured by a lowering of the

reaction temperature at equilibrium. The extent to which this can be done
is limited by the fact that the temperature must be high enough to allow
the reaction to proceed at a reasonable rate. In practice, temperatures of
about 673 K are used. This results in a low yield, but unreacted nitrogen
and hydrogen can be collected and sent back into the reaction vessel again
and again.

2 Pressure

N,+3H, = 2NH,
4 moles 2 moles

An increase in pressure at equilibrium favours the formation of ammonia. For

this reason, the reaction is carried out under pressure. The Haber process uses
high pressures (about 200 atmospheres) to increase the yield of ammonia.

3 Catalyst
In the absence of a catalyst, the reaction has a high activation energy. A
catalyst is used both because it brings the system to equilibrium faster and
because, by lowering the activation energy, it keeps fuel costs down by
allowing the reaction to be carried out at a lower temperature.

(ii) Application of Le Chatefier’s principle to the catalytic

oxidation of sulfur dioxide to sulfur trioxide
In the industrial manufacture of sulfuric acid, the slowest step is the
following reaction:

SO, + 20, = SO, AH =-98 kJ mol

 _ CHEMICAL EQUILIBRIUM.
The process used to make sulfur trioxide is called the contact process. The
sulfur trioxide is the desired product, as it reacts readily with water forming
sulfuric acid:

SO; + H,O > H,SO,

1 Temperature

SO, + %20, = SO, AH =-98 kJ mol!

Since the forward reaction is exothermic, this reaction is favoured at
equilibrium by a lowering of the reaction temperature. In practice, a
temperature of about 713 K is chosen, as this is the lowest temperature that
can be used without reducing the rate to too low a level.
2 Pressure

SOs 1405. = SO;

1% moles 1 mole

The forward reaction brings about a reduction in the number of molecules

present, and so is favoured by high pressures. In practice, a high yield is
obtained using atmospheric pressure or a pressure slightly higher than that,
and so higher pressures are not economically justified.

3 Concentration
The forward reaction is favoured if the sulfur trioxide is removed as it is
formed. Sulfuric acid synthesis plants therefore incorporate a method for
removal of the sulfur trioxide formed, allowing unreacted oxygen and sulfur
dioxide to react further.
4 Catalyst
A catalyst is used as it brings the reactants to equilibrium faster by lowering
the activation energy.

e A reversible reaction is a reaction that can take place in either

direction.
@ Chemical equilibrium is said to be dynamic because, at equilibrium, there
are reactions continually occurring, and the rate of the forward reaction
equals the rate of the reverse reaction.
e@ Le Chatelier’s principle: When a system at equilibrium is subjected to a
stress, the equilibrium shifts in such a way as to minimise the effect of
_ the stress.
 CHAPTER 20
Acids and Bases 2

@@ © Topics Covered in this Chapter

The pH scale
Calculation of pH of solutions of strong acids
Calculation of pH of solutions of strong bases
Solutions of weak acids
Calculation of pH of solutions of weak acids
Solutions of weak bases
Calculation of pH of solutions of weak bases
Choice of indicator and titration curves
Theory of acid—base indicators

The pH scale
The pH scale was developed by Sorensen, a Danish
chemist, in 1909.

Soren Sorensen

Water undergoes reaction with itself to a slight extent as follows: ”

HO + H,O = H,O* + OH
This is called the self-ionisation of water, as one of the water molecules
dissociates into a H* and an OH7 ion. It is found that at 298 K

K,, = [H,0*] [OH-] = 1 x 10-14

where the square brackets denote concentrations in moles per litre. Kas
called the dissociation constant of water. The value of K,,, like any
equilibrium constant, is temperature-dependent. The value of K_,, increases
as the temperature increases and decreases as the temperature decreases.

Since the concentrations of species in aqueous solution are often very small —
for example, [H,O*} = 1 x 10-7 M in pure water at 298 K, and is even less
 ACIDS AND BASES 2.

in basic solutions — a
logarithmic scale is found to be useful in dealing with
such concentrations.

Since H* exists as HO” in solution,

pH = —log,, [H30*]

The square brackets denote concentration in mol |!.

=—\P

At 298 K, the pH of pure water = =10g;, [307]

=—log,, (107) 3
=-(-7)=7
Since K, varies with temperature, the pH of pure water varies also. The pH
of pure water decreases as the temperature increases.

of
|pH
water
pure

‘270-280 ~«290 300310 320-330

; Temperature (K)
Fig. 20.1 The value of the pH of pure water depends on
the temperature ;

RE
ee
PN
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 20.2
Calculate the H;0* concentration of a solution with a pH of 2.

Answer
pH . =~log,, [H,0*] =2
pi =log)¢ the h =!22

[H30*] = antilog (-2)

= 0:01 M

Neutral

Fig. 20.2 The pH scale

The pH scale is not useful outside the 0 to 14 range, as in more

concentrated solutions of strong acids and bases, the acid or base does not
dissociate fully in solution, making a pH calculation difficult.

Universal indicator solution, or universal indicator paper, can be used to

find the pH of a solution. Universal indicator is a mixture of indicators that
changes colour as the pH is changed. The pH of a solution is measured after
adding universal indicator by comparing the colour of the solution with a
colour chart.

The pH of a solution can also be measured using a pH meter. This

instrument gives a numerical reading for the pH directly.

Calculation of pH of solutions of strong acids

Example 20.3
Find the pH of a 0.00004 M solution of hydrochloric acid.

Answer
pH = —log,, [H;0*]
= 10919 (0.00004)
=440
8 ah -Ta _ ACIDS AND BASES2.
Example 20.4
What is the pH of a solution containing 3.15 g of HNO, in 500 cm? of solution?

Answer
The nitric acid solution contains 3.15 g of nitric acid in 500 cm3.
_ 3.15 x 1000 g se
a 500
= 6.3.41.
The molar mass of HNO, is 63 g mol’.
Therefore, [HNO] = 6.3 / 63 mol |"!
=0emoll
Since HNO, is a strong acid, [H30*] = [HNO,] = 0.1 mol I"!
pH = —l0g,, [H;0*]
= -109,, (0.1)
at

Calculation of the pH of solutions of strong bases

In calculating the pH of a strong base, the idea of pOH is used. pOH is
defined as —log, 5 T@lerse

pH = 14-—.p0H

Example 20.5
Find the pH of a 0.001 M NaOH solution.

Answer
[NaOH] = 0.001 mol I!
[OH-] = [NaOH]
pOH =-log,, [OH]
= —log,, (0.001)
=
pH = 14-pOH
= 14-3
iS mls

Example 20.6
What is the pH of a solution containing 0.8 g of NaOH per litre?

Answer
The NaOH solution contains 0.8 g of NaOH in 1 litre.

(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

The molar mass of NaOH is 40 g mol’.

Therefore, [NaOH] = 0.8/40 mol IF!
= 0.02 mol I!
Since NaOH is a strong base, [OH-] = [NaOH] = 0.02 mol I"!
pOH —log,) [OH™]
= —log,, (0.02)
= 1.6990
pH = 14-—pOH
= 14- 1.6990
= 2,300"

Solutions of weak acids

Weak acids when dissolved in water transfer a relatively small number of
their protons to the water, unlike strong acids, for which total proton
transfer occurs. A weak acid such as ethanoic acid (CH,COOH) will react
as follows:
CHj,COOH + H,O = CH,COO-+HOt
At equilibrium,
K, = [CH,COO-] [H,0*] / [CH,COOH]
where K_ is called the dissociation constant of the acid. (The term
ionisation constant is also used for ioe)

In general, a weak acid, HX, has a dissociation constant K, where K, = P|

pO} / {HX}. The weaker the acid, the smaller the value of Ke

Example 20.7 .
Write an expression for the dissociation constant, K,, for the following weak
acid: HNO,.

Answer .
HNO, dissociates in water as follows:
HNO, + H,O = NO; + H,0+
_ [NO5] [H,0*)
2” ~~ THNO,]
 __ACIDS AND BASES 2
Example 20.8
A weak acid, HX, is 3.5% dissociated in a 0.1 M aqueous solution. Find the
value of the acid dissociation constant, Ke.

Answer
The reaction is

HX + H,O = Xo + H,O*

Ignoring the concentration of water, which is present in excess, the initial

concentrations of each of the other species are:

[HX) =X] [H,04]

0.1 @) )

The equilibrium concentrations are:

[HX] x] [H,0*]
0.1 — 0.0035 0.0035 0.0035
= 0.0965 0.0035 0.0035

Substituting these values into the equilibrium constant expression:

K,AX-] JH,07] / {HX] = (0.0035)* / 0.0965 = 1.27 x 107

Calculation of the pH of solutions of weak acids

It is possible to work out the pH value of a solution of a weak acid whose
concentration is known using the formula pH = —logiol (Kas M,) | where
M,, is the concentration of the weak acid in moles per litre. This formula is
based on the simplifying assumption that the concentration of the acid does
not change. This approximation is justified because the extent of
dissociation of a weak acid is small.

Example 20.9
Calculate the pH of a 0.1 M solution of ethanoic acid, given that the K, value
for this acid is 1.8x 10>.

Answer
pH = —logio [ (Ka x Ma) |
= +log,q | f(t.8x10 x0.1)|
= -log,,| Y(0.0000018)|
= -109;9 (0.001342)
=2.87
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 20.10
Find the pH of a solution containing 30 g of CH,COOH per litre of solution.

Answer
The ethanoic acid solution contains 30 g of ethanoic acid in 1 litre.
The molar mass of CH,COOH is 60 g mol-!.

Therefore, | [CH,COOH] = 30 / 60 mol |-1

= 0.5 mol I!
pH —logio| (K3 x M3) |

= tog |VGBx10 e05)4

= -log;.[ /(0.000009) |
= ~log,, (0.001342)
= ~l09,, (0.003)
= 2.59

Solutions of weak bases

Weak bases, like weak acids, only dissociate to a slight extent in water.
Ammonia when placed in water reacts as follows:

NH, + H,O = NH,* + OH”

At equilibrium:
K, = [NH,*] {OH} / [NH,]
K, is called the dissociation constant of the base. (The term ionisation
constant is also used for K,.) The weaker the base, the smaller the-value of K i

Example 20.11
Write an expression for the dissociation constant, K, for the following weak
base: C,H.NH,.

Answer
C,H,NH, reacts with water as follows:
CH.NH, + HO = C,H,NH,* + OH"
K, = [C,H.NH,*] [OH]
[C,H.NH,]
 _ ACIDS
AND BASES 2 © | En
Calculation of the pH of solutions of weak bases
The K, value for a weak base can be used to work out the pH of a solution
of the base, provided that the concentration of the solution is known.
The formula pOH = —logio] (K, x My) | where M, is the concentration of
the weak base in moles per litre, can be used. This formula is based on the
simplifying assumption that the concentration of the base is constant.

Example 20.12
Find the pH of a 0.001 M solution of ammonia, given that the K, value for
this base is 1.8 x 10-5.

Answer
pOH = —log,o| /(Kp x Mp)|
e Hog, 1 8x10>x0.001) |
= log, |V(0.0000018) |
= log, (0.000134)
= 3.872
pH =14—p0OH
= 14 - 3.872
= 10.13

Example 20.13“
Find the pH of a solution containing 6.8 g of NH, per litre of solution.

Answer
The-ammonia solution contains 6.8 g of ammonia in 1 |.
The molar mass of NH; is 17 g mol"!
Therefore, [NH,] = 6.8/17 mol j=!
= 0.4 mol I"!
pOH = ~logio| (Kp XMp) |
= -og, V1.8 10 x0.4)|
= -log,,{ s(0.0000072) |
= —l0gj9 (0.00268)
27570
pH = 14-pOH
14-2572
Sa
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Choice of indicator and titration curves

e@eeeceetcoeoseoee
eee eeoseeocoevnseoeoaegeveoaeenovnevaeeoeoeg

An acid—base indicator is a weak acid or base that has a different colour when it
is dissociated into its ions than when it is undissociated.

In an acid—base titration, a base is added to an acid (or vice versa).

The pH changes slowly at first, then as neutralisation is nearly complete, a rapid

change in pH occurs, followed by a levelling off of the pH. For a strong acid—
strong base titration (where both solutions have a concentration of 0.1 M), the
graph of pH v. cm? of base added shows a rapid change in pH between 4 and
10. Any indicator changing colour in this pH range will be useful for detecting
the end-point of the titration. Therefore, indicators such as methyl orange,
methyl red and phenolphthalein are suitable in this type of titration.
Strong acid v strong base

0 50 100 150 200

Volume of base added (cm?)

Fig. 20.3 pH changes during titration of 0.1 M HCl with 0.1 M NaOH

In the titration of a weak acid—strong base, there is a rapid change in pH

between 7 and 10. Phenolphthalein is the most suitable indicator for this
type of titration. .
Weak acid v strong base
|
j
| |
i

0 50 100 150 200

Volume of base added (cm?)

Fig. 20.4 pH changes during titration of 0.1 M CH,COOH with 0.1 M NaOH
 ACIDS AND BASES 2

In the titration of a strong acid—weak base, the graph of pH v. cm? of

base added shows a rapid change in pH between 4 and 7. Therefore, methyl
orange and methyl red are the most suitable indicators for this type of
titration.
art acid” ¥ weak base

Volume of base added (cm?)

Fig. 20.5 pH changes during titration of 0.1 M HCl with 0.1 M NH,

The titration curve for a weak acid—weak base titration shows a very
gradual change in pH near and at the end-point. There is no sharp
end-point and no suitable indicator, so this type of reaction is not
used to determine the concentration of a solution of a weak acid or a
weak base.

Theory of acid—base indicators

@eeseoeeeoeaecesceeec
ee eoeoeeaeee oe ee ese

Indicators are weak acids and bases that change colour when the pH of a
solution in which they are present is changed. Consider a weak acid
indicator, HIn. In water, this dissociates as follows:

HIn + H,O alia H,O*

The undissociated acid (HIn) has a different colour to that of its conjugate
base In.

The dissociation Constant for the acid is: K,= {In—} {H,0+] / {HIn}
Addition of acid shifts the equilibrium in the reaction
Hin + H,O = In” + H,0*

to the left, resulting in the formation of more HIn. If this occurs to a

sufficient extent, the colour of HIn predominates. Addition of base, on the
other hand, shifts the equilibrium right, forming more In. If this occurs to
a sufficient extent, the colour of In” predominates. ‘
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

If the indicator is a weak base, XOH, its behaviour can be explained as

follows. In water, XOH dissociates:

XOH = Xt + OH”

The undissociated base, XOH, has a different colour to that of the

dissociated form, X*. Addition of acid shifts the equilibrium in the reaction
XOH = X* + OH”

to the right, resulting in the formation of more X*. If this occurs to a

sufficient extent, the colour of X* predominates. Addition of base to a
solution of the indicator shifts the equilibrium to the left, forming more
XOH. If enough base is added, the colour of XOH predominates.

An acid-base indicator is a weak acid or base. that has a -

different colour when it is dissociated into its ions than when it
oS undissociated.
~en,

Ke IOOH] = 1% 10
The pH of a solution is the negative logarithm to the base 10 of the
hydrogen iion concentration. oe
An acid— -base indicator iis a weak acid or base that has a different colour
when it is dissociated into its ions than when
it is undissociated.

Your revision notes

 CHAPTER 21
Water

@@ © Topics Covered in this Chapter

Hardness in water
_ Causes of temporary hardness
“Removing temporary hardness
Causes of permanent hardness
Removing permanent hardness
Water treatment
Sewage treatment
Eutrophication |
Heavy metal pollution

Hardness in water
Hard water is water that will not easily form a lather with soap.
pow Oe

Hardness is caused by dissolved calcium and magnesium salts, e.g. calcium

sulfate (CaSO,,) and magnesium chloride (MgCl). In effect, hardness in
water is caused by calcium and magnesium ions, Ca** ag) and Mg** (aq)

Soap molecules are the sodium or potassium salts of long chain carboxylic
acids such as stearic acid, e.g. sodium stearate (C,,H,,COONa).

C,,H;,COONa + water > C,7H3,COO (4) + Na? aq)

This process releases the stearate ion, which is the active part of soap. If the
water is hard, i.e. containing calcium or magnesium ions, these ions will
immediately precipitate with the dissolved stearate ions forming insoluble
calcium stearate or magnesium stearate. For example, with calcium ions:
Ga wach 2C,7H35;COO
4) > (C,7H3,COO7),Ca,)

These precipitates appear as an unsightly scum in the water. Furthermore,

the effect is to remove the stearate ions from the solution so that they are no
longer available to produce lather and act as soap.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Hardness caused by dissolved calcium hydrogencarbonate, Ca(HCO,),, can

be removed by boiling the water. Such hardness is said to be temporary.
Hardness caused by salts other than calcium hydrogencarbonate cannot be
removed by boiling and is said to be permanent.

_ Temporary hardness is hardness in water that canbe

removed by boiling.

Causes of temporary hardness

Temporary hardness is found in parts of the country where limestone, 1.e.
calcium carbonate (CaCO,) is found in the earth. As rain falls, the water
comes in contact with carbon dioxide in the atmosphere.

As a result, a dilute solution of carbonic acid falls on the ground and seeps
into the earth. In limestone regions, the insoluble calcium carbonate on or
in the earth reacts with the carbonic acid, forming soluble calcium
hydrogencarbonate:
H,CO3/4q) + CaCO3,) > Ca(HCO3)9(aq)

The presence of dissolved calcium ions now means that the water is hard,
with consequent problems such as soap wastage.

Removing temporary hardness

If water containing temporary hardness, i.e. containing dissolved calcium
hydrogencarbonate, is heated or boiled, the following reaction occurs:
Ca(HCO3)a/4q) + heat > CaCO; + CO, + HOW
This means that a precipitate of calcium carbonate is formed. Since the
calcium ions are now combined in an insoluble substance they are no longer
available to react with soap anions. Consequently, the hardness is removed.

An undesirable side-effect of this is that the calcium carbonate precipitate

can stick to the inside surfaces of the vessel involved, perhaps a kettle or
central heating pipes or boiler. The build-up of this substance, called
limescale, can cause problems such as wasting heat or even explosions due
to pipes becoming completely clogged.

Specified Demonstration: Tests on scale

deposits im a kettle
Procedure
1 Place a small quantity of limoescale ‘ eee calc)
2 Add 5 cm? of dilute hydrochloric acid.
 _ _ WATER

3 Quickly connect the test tube to a test tube containing 2 cm} of

limewater to test any gas evolved.
4 Repeat the experiment using methanoic acid, vinegar and water in
turn, instead of hydrochloric acid.
5 The limewater will turn milky when the limescale reacts with the
acidic solutions, showing that carbon dioxide has been released.

Causes of permanent hardness

Permanent hardness is caused by any source of calcium ions other than
calcium hydrogencarbonate as well as by sources of magnesium ions other
than, magnesium hydrogencarbonate. Normally, the chlorides and sulfates
of calcium and magnesium cause permanent hardness. For example, water
acquires permanent hardness by flowing through rocks such as gypsum,
which is mainly calcium sulfate.

Permanent hardness is hardness in water that can

be removed by methods other than boiling (such as
ion exchange).

Removing permanent hardness

Permanent hardness may be removed by ion exchange and by distillation.
Unlike temporary hardness, it cannot be removed by boiling.

Ion exchange involves the water being passed through a cation exchange
resin. The resins used are usually complex sodium compounds, represented
here as Na,R. The calcium and magnesium ions in the hard water swap
places with the sodium ions in the resin.

Na,R,.) + Cara > Car... + 2Na (ea)

+

In this way, the hardness-causing calcium and magnesium ions are removed
from the water and replaced by sodium ions, which do not cause hardness.

Deionisation
e e eo
as,
More advanced ion exchange resins remove all ions from the water. The
resin is a mixture of a cation exchanger, which replaces metal ions in water
by hydrogen ions (H*), and an anion exchanger, which replaces anions in
water by hydroxide ions (OH). The H* and OH™ ions then react with each
other as follows:
Ht + OH’ > H,O

The effect of the resin is that dissolved salts are replaced with the water
molecules formed by the combination of hydrogen and hydroxide ions. The
water is said to have been deionised. (251)
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Deionised water is not quite as pure as distilled water, as the ion exchange
resin merely removes dissolved ions from the water. Distilling the water
removes all dissolved and suspended solids and dissolved gases from the
water.

Temporary hardness may be removed by ion exchange and

- by distillation as well as boiling.
Permanent hardness may be removed by ion exchange and
by distillation but not boiling.

Water treatment
Water treatment plants receive the raw untreated water from a range of
sources such as rivers and lakes. As the water flows into the treatment plant,
it passes through a metal grid or screen that removes floating matter such
as branches, twigs or litter. The water is stored in large tanks where
suspended particles settle to the bottom, before the following procedures
are carried out.

1 Flocculation
A flocculating agent (coagulant) is added to and mixed with the water. This
causes the small, suspended particles to stick together to form larger heavier
particles called flocs. Aluminium sulfate is used for this purpose, though it
is used in conjunction with synthetic polyelectrolytes.

2 Sedimentation
The flocculated water is pumped into the bottom of sedimentation tanks,
so as not to disturb the clearer water at the top. The suspended particles
settle to the bottom. :

3 Filtration
Remaining suspended particles are now removed by filtration. The water is
allowed to fall through beds of graded sand and gravel. The sand in the
filter bed acts as a filter and removes the tiny particles from the water.

& Chlorination

in the treatment plant to get the bacteria down to safe levels. This is done
by chlorination — the addition of chlorine or chlorine compounds to kill
microorganisms by oxidation. Both chlorine and sodium hypochlorite
react with water to form chloric(I) acid, HOCI, which is the active
(252) disinfecting agent.
 _WATER
5 Fluoridation
In Ireland and in some other countries, fluoridation of drinking water is
carried out to prevent tooth decay. The fluoride ion F> is added, usually
using sodium fluorosilicate (Na,SiF,) as its source.

6 pH adjustment
It may be necessary to adjust the pH of the water before it leaves the
treatment plant. Tap water should have a pH in the range of 6-8. If the
water is too acidic, i.e. the pH is too low, lime is added to raise the pH. On
the other hand, if the pH is too high, sulfuric acid is added.

Sewage treatment

| Primary treatment
Primary sewage treatment involves screening and settlement
and is a physical process.

Screening Settling

Fig. 21.1 Primary sewage treatment

2 Secondary treatment
Secondary sewage treatment involves the breakdown by
bacteria of organic matter to less harmful materials.

The waste is oxidised by microorganisms in a trickling filter or in an

activated sludge unit. In a trickling filter, the effluent flows through a bed
of stones where microorganisms digest the nutrients in the presence of air, 1.e.
aerobically. An activated sludge unit also operates aerobically. The effluent is
fed continuously into an aerated tank that is kept oxygenated by mechanical
agitators. Once again, microorganisms decompose most of the organic matter.

After the biological stage, the effluent is subjected to further settlement in

tanks.
2 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Ale denMokilivats
Tertiary sewage treatment involves the removal of
phosphates and nitrates from the effluent resulting from
secondary treatment.

Tertiary treatment is a very costly process. Phosphates are removed by

precipitation. They are reacted with a compound such as aluminium sulfate,
AL,(SO,),, producing an insoluble salt — in this case aluminium phosphate
(AIPO,) — which can be removed by filtration.

The most common method of removing nitrates is biological

denitrification. The effluent containing the nitrates is placed in a tank
that has no free oxygen. Bacteria in the tank require oxygen and they take
it from the only available source — oxygen bonded to nitrogen in nitrate
ions, i.e. NO,” PN il, OLDE words, the bacteria reduce nitrates to
nitrogen gas.

Eutrophication
Eutrophication is caused by the overenrichment of water by nutrients such
as phosphates and nitrates. In effect, the nutrients behave as fertilisers that
increase the growth of plants such as algae in lakes and rivers.

The algae are short lived. As they decay, much of the dissolved oxygen in
the water is used up, leading to the death of many forms of animal life.

Waterways can also be polluted by the run-off of excess fertiliser from

farmland. If the quantity used is not carefully controlled, excess nitrate may
be washed into rivers or lakes by rainwater. Once again, eutrophication may
result.

Heavy metal pollution

Metals with high relative atomic masses such as mercury, cadmium and
lead are known as heavy metals. When recycling is inadequate, quantities
of these elements are dumped, e.g. car batteries containing lead or dry
batteries containing cadmium. Dipositive ions of these metals, i.e. Hg?*,
Cd?* and Pb?*, sometimes get into waterways from industrial effluent and
consequently into drinking water. These elements are cumulative poisons
in that frequent exposure causes a build-up in the body, resulting in serious
health damage.

Before the effluent is run into a waterway, the metal ions can be removed
by means of precipitation. For example, lead(II) hydroxide, Pb(OH),, is
 WATER

insoluble in water, so that if effluent containing Pb?* ions is treated with

calcium hydroxide solution, the lead will precipitate as Pb(OH),:

Baa + 20H (aq) — Pb(OH),,.

Hydroxide precipitation is ineffective for mercury removal, but alternatives

such as carbonate or sulfide precipitation are available.

Water quality
SHOHSHHSPHSH OSH HRESTHESEHRHSHHEHHEHOHSHATHHSHHRHHOGHEHARETHEHROTHERSE
HERES HOHOHESEHOCOESHREOHRHODAY
ROSKHOH

Water quality is controlled by EU legislation. Heavy metal limits have to

be set in waterways because of the toxic effects of metals like mercury,
cadmium and lead. Limits on phosphates and nitrates help to reduce the
occurrence of eutrophication in waterways. Limits are also set for chemical
species dissolved in drinking water.

Hard water is water that will not easily form a lather with soap.
Temporary hardness is hardness in water that can be removed by boiling.
Permanent hardness is hardness in water that can be removed by methods
other than boiling (such as ion exchange). :
Temporary hardness may be removed by ion exchange and by distillation as -
well as boiling. :
Permanent hardness may be removed by ion —— and eedistillation :
but not boiling. ; 2
Primary sewage treatment involves Salalah and settlement and is a
physical process. 2
Secondary sewage treatment involves the breakdown by bacteria =
organic matter to less harmful materials. : Z
Tertiary sewage treatment involves the removal of phosphates andnitrates :
from the effluent resulting from pegulowns treatment. 2

Your revision notes

 CHAPTER 22
Water Analysis

@@®® Topics Covered in this Chapter

Atomic absorption spectrometry (AAS)
Colorimetry
Suspended solids
Dissolved solids
Measurement of pH
Total hardness
Measurement of dissolved oxygen
Biochemical oxygen demand (BOD)

Atomic absorption spectrometry (AAS)

The concentration of a heavy metal in water can be measured using an
atomic absorption spectrometer. In this instrument, the sample to be
analysed is dissolved and introduced into the instrument as a fine spray. It
is heated to a high temperature in a flame, with the result that it is
converted into atoms of the element to be analysed.

A special lamp, whose cathode contains the element whose concentration

is being measured, generates light characteristic of the element. This light
is passed through the atomised sample and a certain amount of the light is
absorbed by the sample. The amount of light at one particular wavelength
that passes through the sample is measured by the instrument. The
amount of light absorbed depends on the amount of the element present.

Table 22.1 Principle and processes of atomic absorption spectrometry

Rineipie.=— = = Brovesses
Atoms in the ground state absorb @ Sample solution is sprayed into
light of a particular wavelength a flame; the sample element
characteristic of the element. is converted into atoms of
Absorbance is directly proportional the element
to concentration. ® Ground state atoms absorb
radiation from a source made
from the element
@ Absorbance is measured
 ___WATER ANALYSIS [

Usesofatomic absonption spectrometry

Atomic absorption spectrometry can be used to detect and measure the
concentration of heavy metals, such as lead and cadmium, that may be
present in water.

Colorimetry
The intensity of the colour of a coloured solution is proportional to the
concentration of the coloured substance present. A colorimeter passes light
of a particular wavelength through a sample of the coloured solution and
measures the amount of light absorbed by the solution.

If the absorbance is measured for a range of solutions of known

concentration of the coloured substance being studied, a calibration curve
may be drawn. This is a graph of absorbance against concentration. The
concentration of an unknown solution of the same substance may then be
obtained. A sample is placed in the colorimeter, the absorbance noted and
the concentration is read off from the graph.
0556

Absorbance

0.1

0.0
0 5 10 15 20 25 30 35

Concentration (ppm)

Fig. 22.1 A calibration curve

The general principle underlying colorimetry is that

the absorbance is proportional to the concentration of
the solution.

A colorimeter may be used to estimate the free chlorine in switnming-pool

water or bleach. When chlorine compounds are added to swimming-pool
water, the active agent is usually chloric(1) acid, HOCI. Chloric(I) acid and
its conjugate base, the chlorate(I) ion ClO”, together make up what is called
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

‘free chlorine’. These species react with iodide ions in solution in the same
way as chlorine itself does, oxidising them to iodine:

Cl 2(aq ) ct 2Kliag) '-: |o(aq) 2KCliaq)

The more concentrated the chlorine in water, the more intense the colour of
the iodine solution formed.

Mandatory Experiment 22.1: Determination of

free chlorine in swimming-pool water or bleach
using a colorimeter
orcomparator poeoeoeeooeReeHRD

(a) Determination of chlorine using a colorimeter

Storage spaces for
filters and cuvettes
Filter

Cuvette
containing
solution

Controls
(reference and test)

Fig. 22.2 A digital colorimeter

Procedure
1 Using a‘250 cm? volumetric flask, dilute 2.5 cm? of Milton sterilising
fluid to 250 cm? with deionised water.
2 Add 5 cm? of 5% ethanoic acid solution to each of five 50 cm?
volumetric flasks, which are labelled A, B, C, D and E, respectively.
3 Use a burette to transfer the diluted Milton solution to the volumetric
flasks as follows: 1.0 cm? to flask B, 2.0 cm? to flask C, 4.0 cm? to flask
D, and 8.0 cm? to flask E.
4 Transfer about 5.0 cm? of 2% potassium iodide solution, i.e. an excess
of KI, to each of the five flasks, and dilute to the mark with deionised
water. Stopper each flask, mix thoroughly and allow about five minutes
for the free chlorine to oxidise the iodide ions to iodine. Colours of
different intensity will result.
5 Switch on the colorimeter and place a 440 nm wavelength filter in the
filter slot. Pour each of the five standard solutions into a cuvette, rinsing
each cuvette first with the solution it is to contain.
6 Zero the colorimeter in accordance with the manufacturer’s instructions.
7 Measure and record the absorbance of each solution.
 WATER ANALYSIS

8 Plot a graph of absorbance versus concentration (in terms of chlorine)

for the five standard solutions.
9 Add 5 cm? of 5% ethanoic acid solution and then 5.0 cm? of 2%
potassium iodide solution to a 50 cm? volumetric flask, labelled F. Fill
the flask up to the mark with the swimming-pool water or diluted
bleach. Allow about five minutes for the colour to develop.
10 Measure and record the absorbance for the solution in flask F.
11 Using the graph, find the concentration of NaOCl in the sample.
12 Multiply by 71 / 74.5 to calculate the concentration of free chlorine in
the sample.

(b)Determination ofchlorine using acomparator

@eeenseeeseesecsess

Free chlorine pies DPD No. 1 tablets (N,N- diethyl-eepheayieneciam netin

the form of its sulfate) to a water-soluble red product. The more concentrated
the chlorine in the water, the more intense the red colour produced.

Fig. 22.3 A comparator

Procedure
1 Use some of the water being tested to rinse the compartments of the
comparator.
2 Fill each compartment with fresh portions of the sample.
3 Adda DPD No. 1 tablet to each compartment, and crush each tablet
with a stirring rod.
4 With the lid fitted, shake the comparator until the tablets have
dissolved completely.
5 Compare the colour produced in the sample with the pre-calibrated
standards built into the comparator.
6 Choose the best colour match, and read the free chlorine concentration
of the selected standard in ppm (mg |").

Uses of colorimetry «
@eeneeoeeosoaese °

Colorimetry can ie tase innif Bdeless peeanin waterPand ofFercilisenst In ahh

case, suitable reagents have to be added in order to produce a coloured solution.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Suspended solids
Turbidity in water is a cloudiness or lack of clarity caused by suspended
particles. These are insoluble substances that are too finely divided to settle
to the bottom but are dispersed throughout the water sample. The
cloudiness may reduce light penetration in surface water and interfere with
photosynthesis in aquatic plants.

Example 22.1
500 cm? of water was filtered and it was found that the mass of the filter
paper had increased by 0.33 g after drying. Calculate the total suspended
solids in the water.

Answer
Total suspended solids = 0.33 g in 500 cm?
i 0.33 x 1000 gh
500 .
= 0.66 x 1000 mg I"'
= 660 ppm.

Mandatory Experiment 22.2(a): Determination

of total suspended solids (expressed as ppm)
in a water sample by filtration
Procedure
1 Find the mass of a dry filter paper.
2 Filter 1 litre of the water sample. ‘3
3 Dry the filter paper in an oven.
4 Find the mass of the dried filter paper. R
5 By subtraction find the mass of suspended solids.
6 Calculate the mass of total suspended solids in mg/l (ppm).

Dissolved solids
Dissolved solids can affect the colour or taste of water. If the amount of
dissolved solids is very high, it may be an indication that the sample is of
salt water.
B a I I SATE ANALYSIS ORD
Example 22.2
100 cm? of a filtered water sample in a beaker was evaporated to dryness and
it was found that the mass of the beaker had increased by 0.055 g after drying.
Calculate the total dissolved solids in the water.

Answer
Total dissolved solids = 0.055 g in 100 cm3
_ 0.055 x 1000 he,
100
= 0.55 x 1000 mg I!
= 550 ppm

Mandatory Experiment 22.2(b): Determination

of total dissolved solids (expressed as ppm)
in a water sample by evaporation
Procedure
Find the mass of a clean dry 250 cm? beaker.
Add 100 cm? of a filtered water sample to the beaker.
Evaporate to dryness in an oven.
Find the mass of the dry beaker when cool.
BR
WA
Fe
WN Calculate the increase in mass of the beaker, which equals the mass
of total dissolved solids in the water sample. Express the result in
mg/l (ppm).

Measurement of pH
The pH of a solution can be measured accurately using a pH meter. A
pH meter consists of three main parts: a pair of electrodes that dip into
the solution being measured, an electronic circuit, and a readout device.
@® The pair of electrodes, usually combined in a single probe, develops
a voltage between them. The size of the voltage depends on the
hydrogen ion concentration and consequently on the pH.
® The electronjc circuit amplifies this voltage sufficiently so that it can
register on a readout device.
@ Most readout devices are digital and the pH is displayed directly.
@ As pH meters are very sensitive instruments, they are easily disturbed
in use or storage. They must be calibrated periodically using buffer
solutions, which are resistant to changes in pH.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

pH meter

5 Glass electrode

Fig. 22.4 pH meter

Uses ofpH meter

te bEeH meters eaelude:
@ Analysis of river and lake water to determine the existence of
pollutants.
@ Measurement of the pH of collected rainwater to test for the occurrence
of acid rain.
@ Measurement of the pH of water in water treatment plants to determine
if pH adjustment is necessary to make the water suitable for use by
consumers.
@ Measurement of pH at regular stages in the course of an acid—base
titration in order to plot a titration curve.

Mandatory Experiment 22.2(c): Determination

of the pH of a water sample .
Procedure ts
SCHROFSHHFSKSSHFSHSTSHSHOHSCHSHSTAHFHHRHOSCHHSSRHOLOHSSSESSRHOSHSERROSOTHHSSSSESHKRESSESSeSeEOoHRaESESEOESES

i aliprere the pH meter and dip the electrode’or probe into sas water
sample. Record the steady reading.
2 Alternatively, add a few drops of universal indicator or dip a strip of pH
paper into the water sample. Compare the colour obtained with the
appropriate colour charts. Record the pH of the matching colours.
3 Repeat for each water sample.

Total hardness
The total hardness of a water sample is estimated by titrating the sample
with a standard solution of the disodium salt of ethylenediaminetetraacetic
acid (edta).
 WATER ANALYSIS

O
F Guimiaca
we OH
fered qremed «
< fe)
CH; G7
OH

CH= G

We OH
Ho="C==-N

i CH
OH
Fig. 22.5 Structure of edta

This reagent forms stable complexes with calcium and magnesium ions
when the pH is >9. This is achieved by adding a buffer solution, i.e. a
solution that resists changes in pH, of pH = 10. The edta reagent can be
used to measure the total quantity of dissolved Ca** and Mg?* ions in a
water sample, in other words, the total hardness.

Since edta cannot distinguish between Ca** and Mg?’* ions, the total
hardness is conveniently expressed as ppm of calcium carbonate
(CaCO,). This is merely a convention and it should be noted that
calcium carbonate is insoluble in water and does not directly cause
hardness itself.

The disodium salt of edta is a primary standard, more soluble in water than
edta itself, and is consequently more commonly used as the reagent than
edta. If Na,H,Y represents this salt, it ionises in aqueous solution to
H,Y*-, which complexes in a 1:1 ratio with either Ca** or Mg** ions
(which are represented as M**). The equation for the reaction is as follows:
He + Met > MY" 2 Fe
»

Solutions of edta should be stored in plastic containers rather than

glass bottles. If the solution is stored in glass bottles, its concentration
will decrease appreciably with time as metal ions are extracted out of
the glass.

The indicator Eriochrome Black T is used to detect the end-point. This

indicator is dark blue in colour, but changes to wine-red when complexed
to calcium or magnesium ions. Thus, when the indicator is added to the
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

water sample, a wine-red colour appears if these ions are present. However,
edta forms a more stable complex with the metal ions, so as the titration
proceeds the metal ions break away from the indicator and complex with
the edta. When this occurs to a sufficient extent, the dark blue colour of the
indicator is restored.

The end-point is detected when the wine-red colour just changes to dark
blue. The reaction between the red indicator—metal.complex and the edta
reagent at the end-point can be represented as follows:
Min- + H,Y2- > Hin? + MY? + H*
wine-red blue

Example 22.3
50 cm? of a hard water sample required 23.85 cm? of a 0.01 M edta solution
for complete complexing of the metal ions. Calculate the total hardness of the
water in ppm of calcium carbonate. Ne

Answer ™

HONE: + M2t+ — MY2- + 2Ht

(The ratio of edta ion : metal ion = 1:1)

V,x M,xn, =V,xM,xn,
50.0 x M,x 1 = 23.85 x 0.01 x 1
M, 223 95.x% 001-8 U/(50.0 x1)
: = 0.00477 moles/litre of Ca2* and Mg?+
: = 0.00477 x 100 g/l CaCO;
= 0.477 g/l CaCO;
= 0.477 x 1000 ppm CaCO; *_
= 477 ppm CaCO,
= total hardness of water sample

Mandatory Experiment 22.3: Estimation of the

total hardness of a water sample using edta
Procedure
1 Rinse the burette with the edta solution, the pipette with the hard
water, and the conical flask with deionised water.
2 Fill the burette to the mark with the edta solution, making sure that the
part below the tap is filled.
 IE
WATER ANALYSIS (D
3 Pipette 50 cm? of the hard water sample into the conical flask and add
2—3 cm? of the buffer (pH 10) solution.
4 Using the spatula, add the solid indicator to the flask in minimal
quantities, with swirling, until a deep wine-red colour is obtained.
5 Carry out one ‘rough’ titration and a number of accurate titrations until
two titres agree to within 0.1 cm°. The end-point is reached when the
colour just changes from wine-red to dark blue.
6 Use the data to calculate the total hardness of the water sample.

Measurement of dissolved oxygen

The dissolved oxygen present in a water sample can be measured by an
iodine—thiosulfate titration, using the Winkler method. Under alkaline
conditions, manganese(II) sulfate produces a white precipitate of
manganese(II) hydroxide:

Mn?** aq + 20H (aq) = Mn(Oh)>.<)

This is then oxidised by the dissolved oxygen in the water, forming a brown
precipitate:

_ 2MN(OH)4)+ On¢4q) > ZMNO(OH)6)

The mixture is then acidified with concentrated sulfuric acid. Under these
conditions, the Mn(IV) oxidises the iodide ions to free iodine:

MnO(OH)) + 4H*4q) + 2 “(aq ,aq) > MN2*aq) + lovaqy

2(aq
+ 3420,
The free iodine is then titrated with standard sodium thiosulfate solution in
the usual way.
2 a is
lytaq + 25293* (aq) > 2h (aq + 5496" (aq)

Overall: |
1 mole O, = 2 moles MnO(OH), = 21, = 4 moles SAG Hams i.e. the ratio of
dissolved oxygen to thiosulfate is 1:4.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Example 22.4
50 cm? of water was analysed for dissolved oxygen using the Winkler method.
The iodine liberated required 15.6 cm? of a 0.004 M sodium thiosulfate
solution for complete reaction. Calculate the dissolved oxygen content of the
water.

Answer
V,x M,x n, = ee
50.0x M,x4 = 15.6 x 0.004'xi4
M, . =15.6x 0.004~x 1/(50.0x 4)
= 0.000312
Concentration of dissolved oxygen = 0.000312 M
= \0.00312/x'32'gN
= 0.009984 g/|
= 9.984 ppm

Mandatory Experiment 22.4: Estimation

of dissolved oxygen by redox titration
Procedure—
1 Re a 250 reas reagent Bone with deionised water, shaking
vigorously to wet the inside and so avoid trapped air bubbles.
2 Immerse the bottle in a basin of the water sample in order to fill the
bottle,*making ae that there are no trapped air bubbles.
3 Add about 1 cm? each of manganese(II) sulfate solution and of alkaline
potassium iodide solution to the bottle, using a dropper placed well
below the surface of the water. This allows the two solutions to sink to
the bottom of the bottle.
4 Stopper the bottle so that no air is trapped — some water will overflow
at this point.
5 Invert the bottle repeatedly for about a minute, and then allow the
brown precipitate to settle out.
6 Carefully add 1 cm? of concentrated sulfuric acid to the bottle, by
running the acid down the side of the bottle.
7 Restopper the bottle, being careful not to trap any air. Redissolve
the precipitate by inverting repeatedly. If not all the precipitate
has dissolved at this point, add a little more acid and repeat the
mixing process. The brown colour of iodine should now be visible.
8 Rinse the pipette, burette and conical flask with deionised water.
9 Rinse the pipette with the iodine solution and the burette with the
sodium thiosulfate solution.
 -___WATERANALYSIS- Oh aS

10 Pipette 50 cm? of the iodine solution into a conical flask and titrate
with 0.005 molar sodium thiosulfate solution.
11 Add about 1 cm? of starch indicator when a pale yellow colour is
present. A dark blue colour is produced and the titration is continued
until this colour just disappears.
12 Carry out a number of accurate titrations until two titres agree to
within 0.1 cm?.
13. Calculate the results in (i) moles of oxygen per litre, (ii) grams of
oxygen per litre, and (iii) dissolved oxygen in ppm.

Biochemical oxygen demand (600)

The oxygen content of water can be assessed by measuring the biochemical
oxygen demand (BOD). This is a measure of the amount of oxygen
required by bacteria to change all of the organic material present in a water
sample to carbon dioxide and water by aerobic oxidation.

The biochemical oxygen demand of a water sample is the

amount of dissolved oxygen in ppm used up by the sample
over a period of five days at 20°C in the dark.

To measure the BOD, an experiment is set up in which a water sample that

is saturated in oxygen is allowed to stand at 20°C for five days. The sample
is kept in the dark to prevent the production of oxygen by photosynthesis
that might be carried out by any plant life present.

The Winkler method of measuring dissolved oxygen is carried out on the

sample of water at the start and end of the five-day period. The difference
between the two results gives the biochemical oxygen demand.

@ The principle underlying atomic absorption spectrometry is that atoms

in the ground state absorb light of a particular wavelength characteristic of
the element. Absorbance is directly proportional to concentration.
The processes involved in atomic absorption spectrometry are: (1) the sample
solution is sprayed into a flame and the sample element is converted into
atoms of the element, (2) ground state atoms absorb radiation from a source
made from the element, and (3) absorbance is measured.
The general principle underlying colorimetry is that the absorbance is
proportional to the concentration of the solution.
The biochemical oxygen demand of a water sample is the amount of
dissolved oxygen in ppm used up by the sample over a period of five days
at 20°C in the dark..,
 CHAPTER 23
Option 1

@@© Topics Covered in this Chapter

® Option 1A: Industrial chemistry
Contributions of chemistry to society
Industrial chemical processes
Characteristics of industrial chemical processes
Industrial Case Study: Manufacture of magnesium oxide
ne,
SRO
LON
from seawater
@ Option 1B: Atmospheric Spear
The atmosphere _
Oxygen
Nitrogen
Oxides of carbon
Carbon dioxide in water
The carbon cycle
Greenhouse effect and global warming
Greenhouse gases
Acid rain
Oxides of nitrogen
Oxides of sulfur
Scrubbing waste gases
The ozone layer | -
Damage to the ozone lave:
ononenononenonenenoneneonen
oonReplacements for CFCs

Option 1A: Industrial chemistry

Contributions of chemistry to society
Useful materials that are being continually produced by the chemical
industry include:
@ In the area of health, medicines and the chemicals needed to make
water safe to drink.
@ In agriculture, crop yields are improved by the use of fertilisers,
herbicides and pesticides.
@ A wide variety of metals, plastics, synthetic fibres, fuels, detergents,
enzymes, dyes, paints, semiconductors, liquid crystals and chemicals
used in food processing.

Industrial chemical processes

A batch process is an industrial process in which an

amount of the product is made in a reaction vessel during a
definite time interval, and is then removed from the vessel.

Batch processes are widely used in the manufacture of pharmaceuticals.

A continuous process js an industrial process in which the

reactants are continuously fed into the reaction vessel, and
the products are continuously removed.

The manufacture of magnesium oxide from seawater is an example of a

continuous process.

A semi-continuous process is an industrial process in

which part of the process is a continuous process and part
is a batch process.

For example, the brewing of beer is a batch process, but the process of
adding carbon dioxide and of bottling the beer is continuous.

Characteristics of industrial chemical processes

1Feedstock
The reactants in an industrial process are called the feedstock. In th
industrial synthesis of ammonia, the reactants are nitrogen gas and
hydrogen gas. Feedstock is produced from the raw materials.

The feedstock is the reactants in an industrial process.

LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

2 Reaction rate
ihe temperature, pressure ane one lia anata ieia! ice reaction
all affect the reaction rate, so the best conditions have to be selected for the
process to occur at the optimum rate.

3 Product yield
The reaction conditions chosen for a chemical reaction in industry must
result in a satisfactory yield. However, as in the industrial synthesis of
ammonia, there may need to be a compromise found between the conditions
for a good yield and the conditions for a satisfactory rate.

+ Co-products
Co-products are the other products formed along
with the main product being manufactured.

Co-products have to be separated from the main products and either

disposed of or, if they are useful, sold or used onsite.

5 Waste disposal and effluent treatment

cays pease oepone olline air emissions, oe Senne of waste ane
in particular of effluent treatment have to be used.

6Quality control
Instrumentation is sellealle in‘Grtiihseay the dani of materials at
various stages of an industrial process. In the industrial synthesis of
ammonia, analyses of the gas mixtures at all stages of ammonia production
can be carried out using gas chromatography and infrared spectroscopy. The
performance of the catalyst can be monitored using these methods.

nen oa inelude Goh conte oP beeardss onsite tiinnee "i thé

staff in first aid and in fire fighting, and safety features incorporated in the
plant. The location of the site is also important. The site should be designed
to allow access by fire engines to central parts of the plant.

8 Costs

Fixed costs in an industrial process are those costs that have

to be paid regardless of the rate of production.
 OPTION1
These include labour costs, plant depreciation, land rental and repayments
on loans.

Variable costs in an industrial process are those costs that

* depend directly on the level of plant output.

These include the cost of heat, electricity and raw materials as well as the
costs of waste disposal.

Methods that are used to reduce costs include the following: use of heat
exchangers, use of catalysts, recycling of feedstock and the sale of useful
co-products.

9 Site location
Sita Pecaulon cHgale take into account OR. source oisenraw Caaveeale the
proximity of a market for the product, the availability of water and of
transport for raw materials and products, and the availability of a suitable
workforce.

10 Construction materials
CCRSSRESEROR OSHS AEEHESEEES

Plant construction aa must not react Sp he Cangas olvcaess

catalysts or products involved in the process. The construction materials
therefore need to be unreactive and resistant to corrosion by the chemicals
with which they come in contact.

Industrial Case Study: Manufacture of magnesium

oxide from seawater
The manufacture of magnesium oxide from seawater is an industrial process
carried out by Premier Periclase in Drogheda, Co. Louth. The process
involves formation of magnesium hydroxide from the reaction of dissolved
magnesium salts in seawater with calcium hydroxide, followed by further
reactions.

Type ofprocess»
The process is continuous, ety herawPacerials Bene fedin ROACE ly
and the magnesium oxide being continuously produced.

Feedstock (raw materials, preparation)

SSERSEHOROKRASSEHOSHSSHEFOREHESTSOHSSESSHOHS HHOEHREESES
PERSO SHEOEHRESSASSH CHHHSHHSTHHFEHHTHOASTHOSHEHAESAEEROEHORSEROEHO
SOND
SO

The feedstock consists of calcium seaKeRe (ies! ac va norificd

seawater. Limestone and fresh water are the raw materials for the calcium
hydroxide. Seawater is, of course, the raw material for the purified seawater.
oy
Ce @ LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Treatment of raw materials

The limestone is very pure calcium webouaee and issicsiched, ne washed
before being heated in a limekiln to form calcium oxide (quicklime):

CaCO3.. > CaO + COr)

Fresh water is then added to the quicklime to produce calcium hydroxide:

CaO, + H,0, > Ca(OH),,2(aq)

The seawater is taken from the Boyne estuary and stored in a large reservoir,
where sand and other solid impurities settle out. It is then pumped to the
Premier Periclase plant.

The seawater is acidified with sulfuric acid and passed downwards through
a tower against a rising current of air which removes carbon dioxide. Excess
sand and other particles are then removed from the seawater by a settling
process.

Reaction rate and product yield

In the reaction of seawater with calcium hydroxide, soluble magnesium ions
(Mg**) form a precipitate with hydroxide ions from the calcium hydroxide:

MgCl (aq) + Ca(OH)9/24) — CaCl 2(aq)

+ Mg(OH) 2(s)

The reaction, which is very rapid, is carried out in large circular tanks. The
reaction in which magnesium hydroxide is converted into magnesium oxide

Mg(OH),... > MgO.) + HO.

is carried out in a multiple hearth furnace. A high temperature.(900°C) is
used. This increases the rate of reaction. In the furnace, there are three
stages: 3
@ Removal of the remaining water from the wet magnesium hydroxide
@ Reaction to form magnesium oxide at 900°C
@ Cooling

The fine powder that leaves the furnace is converted into pellets under
pressure. The pellets are fed into kilns where at a very high temperature the
magnesium oxide changes into larger crystals. The kilns transform low-
density magnesium oxide into high-density sinter magnesium oxide
(periclase). This product has a buff-brown colour and is chemically
unreactive.

The yield of magnesium oxide is approximately 2 g from each litre of

(272) seawater.
 __OPTION 1 _
Co-products(separation,disposal orsale)
The main co-product is elem chloride, ena is ina Solaraoatin ae eed
seawater. There are at present no commercially profitable co-products from
the Premier Periclase process.

Wastedisposal and effluent control

Dat is removed Bota action gases using electrostatic BiSeHIaES
Following this, the gases are scrubbed with water. This process removes
sulfur oxides and some grit. Used seawater contains some calcium
hydroxide which is neutralised using fresh acidified seawater. The water is
then filtered and pumped out to sea.

Extensive environmental monitoring is carried out in the plant; for example,

monitoring of waste gases for dust and sulfur oxides, and monitoring of
effluent for pH and suspended solids.

Quality control
Analyses of earples are carried Out at various$ stages of the process, using,
for example, automated acid—base titrations.

Safety
There is a Goo Sani programme for staff onsite.pilaeards: arearenes
monitored and engineering work is carried out to make dangerous or
moving machinery safe. Personal protective equipment is used when
required.

Costs
The fixed costs include labour costs, plant maintenance and pliant depreciation.
The variable costs include the cost of electricity, fuel and materials, and the
costs of waste disposal.

Cost reduction can be achieved in a number of ways. For example, heat from
waste gases can ,be reclaimed and used to preheat the intake air to the
limekiln.

Sitelocation
Fe lection « the Bremiée périclesstsite issentble for a auteSed ofireasons?
® There is a highly skilled workforce available
®@ The site is close to a plentiful supply of limestone
@ The site is close to a. supply of seawater
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

®@ The site is convenient for rail, road and sea transport

@ The site already had suitable equipment (e.g. large rotary kilns),
which was previously used for cement making

Suitable materials for the construction ofthe plant

The lime rotary eine ne a eel outer ane with reed ele bec
(i.e. bricks with a very high melting point). The sintering kiln is made of
higher-quality refractory bricks because of the higher temperatures used.
Acid-handling equipment in the plant is made of stainless steel. The
reactors, in which calcium hydroxide and magnesium hydroxide
respectively are formed, are made of concrete.

Uses of‘product
Bee Bpeticlase es a veryrato inticgs poink “(2800°C). Hew ened
periclase is chemically unreactive. It is therefore suitable for use as a heat-
resistant material in the walls of furnaces, for example in steel making.

Option18:Atwosphetic chemistry
The atmosphere
The lowest part of the atmosphere is the troposphere, which is the layer
within 15 kilometres of the Earth’s surface. The troposphere contains about
90 per cent of the air in the atmosphere. The stratosphere is the layer of the
atmosphere immediately above the troposphere.

Dry air contains approximately 78 per cent nitrogen (N,,), 21 per cent oxygen
(O,) and 1 per cent argon (Ar). It contains about 0.03 per cent carbon dioxide
(CO,), although this amount is known to be increasing. Air usually contains
a eae but varying quantity of water vapour.

Fractional distillation of‘oxygen andnitrogen

flee process OF econ eieclindone is used to Shears Sees ee a
nitrogen gas from air. Air must be liquefied before it can be fractionally
distilled. This liquefaction occurs by a combination of increasing the
pressure and lowering the temperature.

The air is first filtered to remove dust. It is then compressed and carbon
dioxide and water vapour are removed. Next, the air is cooled to about 103 K.
It is then cooled further by allowing it to expand suddenly. This cools the air
to a sufficient extent to liquefy it.

Liquid air is mainly a mixture ofliquid nitrogen, which boils at 77 K, and

liquid oxygen, which boils at 90 K. The liquid air is allowed to boil off
 OPTION 1

through a fractionating column. The nitrogen, having a lower boiling

point, boils off first. The oxygen then boils off when the temperature
reaches 90 K.

The most Aimposcant industrial use of oxygen is in steel making, where it is

used to burn impurities out of molten iron. Pure oxygen is used with ethyne
in oxyacetylene torches, which are used for cutting and welding metals.
Oxygen is given in hospitals to patients who suffer from lung conditions to
make it easier for them to breathe.

Nitrogen
@easeeeeene2 6

Nitrogen, at 78 per cent, is by far the most abundant substance in the

atmosphere. It occurs free in nature as the diatomic gas, N,, with the two
nitrogen atoms. joined by a covalent triple bond. The bond energy of the
N=N bond is very large, which means that a lot of energy is needed to break
the bond. Consequently, nitrogen is very stable and chemically unreactive.

When oil tankers empty their cargoes, nitrogen gas, being inert, is used to
flush out the explosive vapours from their tanks. The tanks remain full of
nitrogen until they are refilled with their next cargo of oil.

Food is kept fresh by storing it in nitrogen. In the consequent absence of

oxygen, the microorganisms that cause food to go off are unable to survive.
Thus, the food remains fresh for a longer period.

Pics Seaton,
_ Nitrogen fixation is the conversion of atmospheric nitrogen
to seerpouriae that are used by plants.

The nitrogen
0 cycle
The nitrogen eycle Ahens iy the ie of Gieroges inache Ames ator
does not change. Some nitrogen is removed from the atmosphere by
bacterial nitrogen fixation. More is removed by the action of lightning
followed by rain. Some atmospheric nitrogen is used in the manufacture of
artificial fertilisers. However, certain bacteria convert nitrates in soil into
nitrogen gas, which is released back into the atmosphere to begin the
nitrogen cycle again.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Bacterial Manufacture of
Action of lightning Bacterial fixation
decomposition artificial fertilisers
followed by rain of nitrogen
of nitrates

Nitrogen compounds in soil

Death and decay

Death and decay

Nitrogen compounds in plants or excretion

Eaten as food

Nitrogen compounds in animals

Fig. 23.1 The nitrogen cycle

Oxides of carbon
When carbon is burned in a limited supply of oxygen, incomplete
combustion occurs and carbon monoxide is formed:

Cig BOs. 2(g) CO,

Carbon monoxide is a neutral gas that is also formed when the incomplete
combustion of hydrocarbons occurs. It is a deadly poison, which prevents
the uptake of oxygen by the haemoglobin in blood.

Carbon monoxide has no smell or colour, does not irritate the lungs or the
eyes, so it can easily be breathed in without being noticed. Carbon
monoxide is emitted through vehicle exhausts, particularly in the absence
of catalytic converters, and is also found in cigarette smoke. =

When carbon is burned in excess oxygen, complete combustion occurs and

carbon dioxide is formed:
Cy)(s) + O44) > CO34)

Carbon dioxide is also formed when complete combustion of hydrocarbons

occurs. In brewing, carbon dioxide is a co-product in the production of
ethanol by fermentation:
CEH,
0 Gag) > 2C,H-OH
(24) + 2CO0 46)

Carbon dioxide is an acidic gas, which is used to make fizzy drinks. It is

dissolved in water under pressure, with the result that bubbles of gas are
produced when the container is opened.
 __OPTION
1 ©}
Specified Demonstration: The effect of carbon (or
dioxide on universal indicator solution 3

procedure
1 Place about 25 cm? of universal indicator into a 100 cm? beaker and
dilute with an equal volume of water. Place the beaker on a magnetic
stirrer, add a pellet and start the stirrer at a slow speed.
2 Place a few marble chips in a test tube. The test tube has a two-holed
stopper, with a delivery tube dipping into the beaker, and a teat pipette
containing dilute HCl. The end of the delivery tube should be well
below the surface of the universal indicator.
3 Add dilute HCl from the teat-pipette, a few drops at a time.
4 As the carbon dioxide bubbles through the indicator, a series of colour
changes can be observed.

Carbon dioxide in water

Carbon dioxide is fairly soluble in water:
CO,/,) + excess HO = CO,,,4)

A small proportion of dissolved carbon dioxide reacts with the water to

form carbonic acid, jeFG,ON

COo(4q) + HO, = H,CO3(2)

Carbonic acid

As this is a weak acid, it dissociates to a small extent in aqueous solution:

H,CO3.4q) H"(aqy # HCOS (ag)

Carbonic acid Hydrogencarbonate ion

The hydrogencarbonate ion, HCO,,, is itself a weak acid so further

dissociation can occur, but to a lesser extent:
es Ss 2-
HCO, ava Fiver 1s CO; (aq)
Hydrogencarbonate ion Carbonate ion

This is more likely to occur under alkaline conditions.

The carbon cycle

The carbon cycle indicates why the level of carbon dioxide in the atmosphere
does not change greatly over short periods of time. Some carbon dioxide is
removed from the atmosphere by dissolving in rain or in ocean water.

The major process by which atmospheric carbon dioxide levels are reduced
is photosynthesis. Atmospheric carbon dioxide is used by green plants in
photosynthesis to make more complex carbon compounds. These may be
eaten by animals, which digest them and use them for energy in respiration. 277)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Alternatively, they may be used by the plants themselves in respiration. In

both cases, carbon dioxide is formed and returned to the atmosphere.
Another way that carbon dioxide is returned to the atmosphere is when
fossil fuels are burned.

Greenhouse effect and global warming

@eeoeoeees eeseevpeeoecoeae ooeogcoceeeovuaovnaeaeea

The sun emits energy, some of which is absorbed by the Earth. This
absorbed energy heats the Earth, and the Earth in turn radiates energy,
mostly infrared, back into space. Some gases found in the atmosphere
absorb infrared radiation, thus preventing it from escaping into space. The
effect of this is to make the Earth warmer.

This trapping of heat in the atmosphere is referred to as the greenhouse

effect. It keeps the Earth at a comfortable temperature and makes life, as we
know it, possible.

Problems arise when growing amounts of certain gases in the troposphere

enhance the greenhouse effect. There is now a great deal of evidence that the
Earth is getting hotter, i.e. that global warming is taking place, and that
emissions of greenhouse gases caused by human activities are responsible.

It is widely accepted that the enhanced greenhouse effect will change

weather patterns. Among the effects predicted are: warmer weather,
particularly in high latitudes; changes in prevailing winds and in rainfall
distribution; rising sea levels with consequent flooding and loss of land.

Greenhouse gases
Goce roaoowoovoevoe
vd egneeoes

Werke vapour, carbon dioxide, methane and chlorofluorocarbons are the

most significant greenhouse gases. Water vapour is so abundant in the
atmosphere that it makes the largest contribution to the greenhouse effect.
Global warming causes the amount of water vapour in the troposphere to
increase by evaporation of the oceans. However, the precise effects of this on
climate are not clear.

The amount of carbon dioxide in the troposphere has been increasing for the
past 150 years, largely as a result of the widespread combustion of fossil
fuels such as coal and oil. The destruction of the world’s forests makes the
problem worse because it reduces the amount of photosynthesis taking
place, which would otherwise use up some of the carbon dioxide.

Methane gas (CH,) is produced in marshes, compost heaps, rubbish dumps,

rice paddy fields, biogas digesters, and in the digestive tracts of animals
such as cattle. The concentration of methane in the troposphere is rising.
However, if the methane passes through the troposphere into the
 OPTION 1

stratosphere, it helps to solve the problem of damage to the ozone layer by

chlorine atoms.

Chlorofluorocarbons (CFCs) have a large greenhouse factor but concentrations

are small and decreasing. Apart from their contribution to the increased
greenhouse effect, CFCs are notorious for damaging the ozone layer.

Acid rain
Unpolluted rainwater is slightly acidic. It has apH of approximately 5.7
due to the acidic gas, carbon dioxide, in the atmosphere. Emissions of acidic
gases into the atmosphere lead to a lowering of pH, with the formation of
what is referred to as acid rain. This acid rain damages soil, poisons fish,
attacks trees and erodes buildings. The main causes of acid rain are oxides
of nitrogen and oxides of sulfur.

Oxides of nitrogen
@eeeooecee
ee 8

Oxides of nitrogen are released from car exhausts and power plants where the
high temperatures bring about the oxidation of atmospheric nitrogen. They
are also formed in some biological processes and by lightning discharges.

Nitrogen monoxide (NO) is quickly oxidised in air to nitrogen dioxide

(NO,). Nitrogen dioxide dissolves in water and reacts to form a mixture of
nitrous acid (HNO,) and nitric acid (HNO,):

2NO
9g) + HO” > HNO,/,4) + HNO3,4)

When this occurs in the atmosphere, the result is acid rain.

Oxides of sulfur
@eeeeneoeaeoe eee

Orde of sulfur are mainly formed by the combustion of fossil fuels,

particularly coal. They can also be released by volcanoes and by the decay of
organic matter.

Sulfur in fossil fuels forms sulfur dioxide (SO,), which is a dangerous

pollutant. Sulfur dioxide dissolves in water to form sulfurous acid (H,SO,):

SO, g) + H20q ) > H,SO03,

In the atmosphere, sulfur dioxide is oxidised to sulfur trioxide (SO,). Sulfur

trioxide dissolves in rainwater to form sulfuric acid (H,SO,).
$0 3/4) + HO, — H5SOqaq)

Thus, the release of SO, into the atmosphere is likely to result in rain
containing H,SO, and H,SO,.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Specified Demonstration: The effect of sulfur

dioxide on universal indicator solution
Procedure
1 pice Asan 25 cm: ae sth etal ie intoa 100 ane Palen ee add
an equal volume of water. Place the beaker on a magnetic stirrer, add a
pellet and start the stirrer at a slow speed.
2 Place a spatula full of sodium sulfite in a test tube. The test tube has a
two-holed stopper, with a delivery tube dipping into the beaker, and a
teat pipette containing dilute HCl. The end of the delivery tube should
be well below the surface of the universal indicator.
SS) Add dilute HCl from the teat-pipette, a few drops at a time.
4 As the sulfur dioxide bubbles through the indicator, a series of colour
changes can be observed as the pH drops.

Scrubbing waste gases

Limestone is used to reduce sulfur dioxide emissions from coal-fired power
stations. Coal is mixed with finely ground limestone. The high temperatures
in the furnace cause the limestone to decompose:
CaCO3,. = CaO., + CO54)

The calcium oxide reacts with much of the sulfur dioxide forming calcium
sulfite:
Cad.) + SO3(g) = CaSO3..

This prevents the release of sulfur dioxide into the atmosphere. The process
is called scrubbing.

The ozone layer ,

Gone (O,) is a form of oxygen with three oxygen atoms. It is eee in the
stratosphere by the following photochemical reactions (reactions caused by
light energy):

Oo() + energy > O°(g) + O')

rq) + O%q > O3@)
In the first of the two reactions, radiation from the sun splits oxygen molecules
into high-energy oxygen atoms. In the second reaction, oxygen atoms (O°)
combine with oxygen molecules (O,) to form ozone molecules (O,).

The ozone produced absorbs ultraviolet radiation from the sun to re-form
diatomic oxygen, O,. This reaction is the photodissociation of ozone:

O3g) + UV > O74) + O')

 _OPTION1
In this way, ozone acts as a sunscreen by absorbing the ultraviolet radiation,
which is damaging to plants and animals when it reaches Earth. Ultraviolet
radiation causes sunburn and ultimately skin cancer in humans.

Ozone is also removed from the stratosphere by nitrogen monoxide (NO).

Oxides of nitrogen enter the atmosphere as a result of biological activity and
also during the combustion of fossil fuels. Ozone is also removed by reaction
with atoms of oxygen, where an oxygen atom and an ozone molecule
produce two molecules of oxygen.

Ozone is being made and destroyed all the time and a balance exists to
maintain the ozone concentration. This balance is upset when certain
substances get into the stratosphere.

Damage to the ozone layer

Chlorofluorocarbons or CFCs are substituted hydrocarbons such as CCL.
and CCL,F.

Because of their unreactive nature, CFCs are extremely useful compounds.

Apart from their original use as refrigerants, they are also useful as air-
conditioning gases, as aerosol propellants and as fire extinguishers.

The stability of CFCs and their insolubility in water means that they remain
a long time (i.e. have a long residence time) in the troposphere, where they
have a large greenhouse effect.

Having spent a long time in the troposphere, CFCs eventually reach the
stratosphere where they are broken down by the sun’s ultraviolet radiation.
The reaction results in the release of chlorine atoms from the CFC molecule.
The chlorine atoms produced remove ozone:

CI") + O34) = ClO*,) + 05%)

The chlorine oxide radicals (C1O*) formed in the reaction then react with
oxygen atoms to regenerate chlorine atoms:

s ClO") 4 Oe = a O59)

The net effect is that a chain reaction occurs. Consequently, one CFC
molecule may destroy 100,000 ozone molecules. Chlorofluorocarbons are
the main cause of damage to the ozone layer.

Methane molecules have a greenhouse effect in the troposphere, but when

they reach the stratosphere, they react with chlorine atoms:
CHa) 4k Cire = CH," ¢g)ap HCl)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

This reaction has the effect of removing individual chlorine atoms from the
stratosphere by changing them into hydrogen chloride gas (HCl). Since
hydrogen chloride does not destroy ozone, the overall result of the reaction
is protective of the ozone layer.

However, winter conditions over the Antarctic bring about a situation

where HCl changes into chlorine molecules. These remain in the
stratosphere until ultraviolet light splits them into atoms, with subsequent
serious depletion of the ozone layer over the Antarctic.

Replacements for CFCs

Concern about the effect of CFCs on the ozone in the stratosphere has led to a
severe reduction in their use. Replacements include hydrochlorofluorocarbons
(HCFCs) such as dichlorofluoroethane (C,H,CLP). These molecules contain
C — H bonds, which are broken down in the troposphere. This initiates the
breakdown of the entire molecule, with the result that the chlorine in HCFCs
is unable to reach the stratosphere. Work is continuing to find substitute
compounds and to develop technology aimed at the recovery and recycling
of CFCs. -

Other compounds being used to replace CFCs are alkanes and

hydrofluorocarbons (HFCs). Like HCFCs, these compounds are broken
down in the troposphere. One example of a HFC is tetrafluoroethane
(CEDECE?).

@ A batch process is an industrial process in which an amount of the

product is made in a reaction vessel during a definite time interval, and is
then removed from the vessel. 5g
A continuous process is an industrial process in which the reactants are
continuously fed into the reaction vessel, and the products are
continuously removed.
A semi-continuous process is an industrial process in which part of the
process is a continuous process and part is a batch precess.
The feedstock is the reactants in an industrial process.
Co-products are the other products formed along with the main product
being manufactured.
Fixed costs in an industrial process are those costs that have to be paid
regardless of the rate of production.
Variable costs in an industrial process are those costs that depend directly
on the level of plant output.
Nitrogen fixation is the conversion of atmospheric nitrogen to compounds
that are used by plants.
 CHAPTER 24
Option 2

@e@eTopicsCoveredinthisChapter ==>
— @ Option 2A: Materials
Crystals: ionic, molecular, metallic, covalent macromolecular
Buckminsterfullerene
X-ray determination of structure
Addition polymers
Polymers of substituted alkenes
Discovery of polythene
Discovery of poly(tetrafluoroethene) — Teflon
Recycling of plastics
Metals,
O00000000°0
Alloys
@ Option 2B: Electrochemistry and extraction of metals
The beginnings of electrochemistry —
The electrochemical series
Electrolysis of molten salts
Corrosion and its prevention
Extraction of sodium — the Downs cell
Extraction of aluminium from bauxite
Anodising
Recycling of aluminium
Transition metals
Manufacture of iron and steel
Electric arc process for steel manufacture
O
©:
O-O,
0;
O70.
©
@
O.0.0/
Environmental aspects of iron and steel production

Option 2A: Materials

Crystals
A crystal is a solid in which the atoms, ions or molecules of which it
~ is composed are arranged in a regular three-dimensional structure.
So @ LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Different types of crystal are summarised in Table 24.1.

Table 24.1

lonic Positive and lonic bonds Sodium

negative ions ate chloride
a my ba, ch Molecular Molecules van der Waals’ forces _lodine
&
ee

‘
BAK

a
=
(non-polar) ‘
—oo mAs
=“
ve*“~, Molecular (polar) |Molecules van der Waals’ forces _ Ice
fo
oe- and dipole-dipole
attractions

Metallic Positive ions Metallic bond Sodium

Covalent Atoms . Covalent bonds Diamond,
macromolecular ~ (sometimes with van graphite
. é ~ der Waals’ forces) =

The properties of different types of crystal are summarised in Table 24.2.

Table 24.2

lonie..*. Hard, but High Conducts when — Usually

brittle. ov molten or in dissolves in
solution polar solvents
Molecular Relatively Low Non-conductor Depends on
weak the type of
7 molecule
Metallic Most are Variable Good Insoluble
~ hard, though conductors except in
malleable a mercury
and ductile art See eli ;
Covalent Usually hard = High Non-conductor — Insoluble
macromolecular (except graphite)

Buckminsterfullerene
Until the discovery of fullerenes, scientists believed that only two allotropes
of carbon, namely diamond and graphite, existed. In the mid-1980s, the
English chemist Harry Kroto and his American colleagues Robert Curl and
 OPTION 2

Richard Smalley used a laser to vaporise atoms from a solid graphite disc.
The atoms were allowed to cool and condense in the vapour phase and were
then studied using mass spectrometry. By this means they discovered a
different allotrope of carbon consisting of 60 atoms bonded together in a
structure like “a football. This C,. structure was given the name
buckminsterfullerene.

Fig. 24.1 Buckminsterfullerene

X-ray determination of structure

eeeeanesee

When X-rays are directed at the surface of a crystal, they are scattered from
the surface. The pattern that is detected from the scattering — a diffraction
pattern — can be used to work out the structure of the crystal.

William and Lawrence Bragg

The British father and son team of William and Lawrence Bragg
developed the use of diffraction patterns to work out the structure of
crystals. They received a Nobel Prize for working out the structure of
sodium chloride. ;
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Another Nobel Prize winner who used X-ray

crystallography was Dorothy Hodgkin. She
determined the crystal structure of the complex
organic molecule, penicillin, using an electronic
computer to carry out the complex calculations
involved. Hodgkin later worked out the structure
of vitamin Big

Dorothy Hodgkin

Addition polymers

A polymer is a large molecule made up of many identical

repeating units called monomers.

Alkenes are the raw materials in the industrial manufacture of plastics. In

the polymerisation of ethene, the molecule adds to itself to produce a
saturated hydrocarbon chain that consists of repeating -CH,CH,— units.

H H H H H H
“ J heat, | | |
a wh | i] 1

2n y
C= Cee
catalyst
CSG
yy Pa Peis ona
a. H H H H H
— — Ae

The resulting solid substance is called poly(ethene) or polythene and has

many uses. Polythene is an example of a polymer, a large molecule made
up of many identical repeating units called monomers.

Depending on the conditions used, two forms of polythene can be

produced: low-density polythene and high-density polythene.

low-density polythene ;
This type of polythene has a significant degree of branching. This prevents
the molecules from packing closely together. Because the molecules take up
more space, the density of the polymer is reduced. Low-density polythene
is very flexible and melts at about 360 K.

High-density polythene
There are few side branches in this form of polythene and hie alone the
molecules to pack more tightly. Because the molecules take up less space,
 _OPTION2 OU
the density of the polymer is increased. High-density polythene has a
higher melting point, about 400 K. It is more rigid than low-density
polythene.

Polymers of substituted alkenes

1Poly(chloroethene) —
fotoroechene (CH, -CHCl) polyieriscet £5 form poly(chivreemnene ine
polymer also eeeables poly(ethene), but this time every second carbon in
the chain has a chlorine atom attached. The polymer is commonly known
as PVC.

H Cl peta e Waele
Qn ete ba CC eG
a : are gs ae
H H H H H H |

CHSCSHORTER TERE BEOTEOHeeHes

Phenvieciens in ais one 68 the enon atomsSie aphenyt Agi CcH A)

attached, polymerises to form poly(phenylethene). In this polymer, every
second carbon in the chain has a phenyl group attached. The polymer is
commonly known as polystyrene.

H fe) (0)
a heat C
N= [a cm
catalyst |

alae
efey
G2 H ——
15
aE
a

CHES EOHSEHOSEERESESC
OO SHOH OHH HHOSEOHEEHREOHEOTHO SHOES HEHEHEHEHHSHSHHEHOHHEOHTOEEOESEHREKHEOS

Tetrafluorethene, in which all four Rydrocenatoms in the parent Echene

molecule have been replaced by fluorine atoms, polymerises to form
poly(tetrafluorethene). In this polymer, each carbon in the chain has two
fluorine atoms attached. The polymer is commonly known as Teflon
or PE.

F F ae ees eed co
\ _
C=C
/ heat
pressure
G
|e G G
anal (Gs
2n
y catalyst | | | |

A F oF F F
 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

#Poly(propene) I o@

Propene, CH,=CHCH,, polymerises to form poly(propene). This product

differs from polythene in that every other second carbon in the chain has a
methyl group attached.

7 CH; | H CH H CH; A
heat, | |

cea 2n aeen © ee (Gpemem fe sfc.

es y catalyst | | |

H H ‘HoteHathte BAe

Table 24.3

Ethene Poly(ethene) Polythene Low density:

plastic bags,
he squeezy bottles;
High density:
4 buckets, lunch
boxes
Chloroethene — Poly(chloroethene) Polyvinyl- Garden hoses,
chloride (PVC) window frames,
gutters
Phenylethene —_ Poly(phenylethene) Polystyrene Insulation,
packaging
A

Tetrafluoro- Poly(tetrafluoroethene) Teflon (PTFE) Non-stick

ethene ° 2 coating, artificial
arteries and
veins, plumbing
f tape ~
Propene Poly(propene) Polypropylene Ropes, stacking
chairs

Discovery of polythene
Polythene was discovered by accident in 1933. The British chemists Eric
Fawcett and Reginald Gibson were studying the effect of high pressure
on chemical reactions. At the end of one experiment involving ethene,
carried out at high temperature and pressure, the walls of the reaction vessel
were found to be coated with a white, waxy solid. This solid was recognised
to be a polymer of ethene.

288
High-density polythene was discovered as a result of
the work of the German chemist Karl Ziegler in the
early 1950s. He discovered that certain organic
catalysts, which had metal atoms in their molecules,
allowed polythene to be manufactured at lower
pressures and therefore more economically.

Karl Ziegler

Discovery of poly(tetrafluoroethene) - Teflon

In 1938, the American chemist Roy Plunkett opened
a cylinder of the gas tetrafluoroethene and found a
waxy white powder inside. He realised that the
tetrafluoroethene gas molecules had combined in a
polymerisation reaction.

Poly(tetrafluoroethene), later called Teflon, was found

to have some remarkable properties, which were not
affected by extreme temperatures. It was inert and also Roy Plunkett
had a slippery feel.

Recycling of plastics
Polystyrene is a completely recyclable plastic. After collection, it is sorted
from other plastics to allow separate recycling.

After sorting, the polystyrene is shredded and then washed and dried.
Finally, it is re-extruded, that is, melted and forced under pressure through
a moulding device.

Metals
Table 24.4

ce

Most metals are hard Some solid non-metals are hard but brittle
and have relatively low melting points

Most metals have lustre Non-metals do not have lustre

Metals are malleable and ductile |Non-metals are neither malleable nor ductile

Metals are good conductors of | Non-metals are good insulators

heat and electricity
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Alloys

An alloy is a mixture of two or more elements, at.

least one of which is a metal.

The elements are usually mixed by melting them, mixing the molten
elements, and then allowing the mixture to solidify.

Table 24.5

Brass | Copper and zinc

Bronze: /)..0 Copper and tin
Stainless steel Iron, chromium, nickel and carbon

Steel contains mainly iron with, typically, about-0.3 per cent of carbon and
small, carefully. measured amounts of transition metals such as chromium,
nickel, tungsten, titanium, vanadium and manganese. These elements are
chosen to give the steel particular properties to suit its use, such as hardness,
rigidity, flexibility. and resistance to corrosion. Steel is much harder than iron
and can be used in making cutting tools, girders for bridges and steel-framed
buildings, and reinforcements for building foundations, amongst many
other uses.

Option 26: Electrochemistry and extraction of metals

The beginnings of electrochemistry
In Italy in 1786, Luigi Galvani noticed that a dissected “frog’s leg
twitched when it came into contact with two different metals.

Luigi Galvani
 OPTION 2

Alessandro Volta stated in 1794 in Italy that the frog

leg twitched because of the difference in potential
between two dissimilar metals connected by the
animal tissue. He found by experiment that electricity
flowed when two different metals were used without
any animal tissue present. By 1800, he had gone on to
invent the first practical battery — the Voltaic pile.

Alessandro Volta
Volta’s battery used cells composed of two different metals, for example
silver and zinc. These batteries produced a useful electric current.

Humphry Davy in London in the early 1800s

improved the design of the Voltaic pile, and developed
more powerful batteries. In the years 1807-1808, he
discovered several elements, including potassium and
sodium, using electrochemical methods.

Humphry Davy

In London during the years 1833-1836, Michael

Faraday discovered the laws of electrolysis, including
the proportionality between the mass of product
deposited during electrolysis and the current passed.

Michael Faraday
The electrochemical series
@eeecoeooaoecoaoecoo
eee eo eee eeve eae

In most cases, the higher a metal is in the electrochemical series, the more
reactive it is. The position of a metal in the series relative to another may
be determined experimentally. For example, to establish the relative
positions of zinaand copper, a piece of zinc is immersed in a 1 M solution
of a water-soluble zinc compound, such as zinc sulfate.

The piece of zinc is then connected by means of a wire through an ammeter

to a piece of copper immersed in a 1 M solution of a water-soluble copper
compound, such as copper sulfate. The two solutions are connected by
means of a salt bridge that contains a solution of an electrolyte. Electrons
flow through the wire from the metal that is higher in the series to the other
metal, causing a deflection in the ammeter.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Electrolysis of molten salts

The electrolysis of molten lead(II) bromide is carried out using carbon or
platinum electrodes. The electrolyte is composed of Pb?* ions and Br ions.
The Pb? ions move to the cathode, where they are reduced:
Ph** if Zee PDa

The Br ions move to the anode, where they are oxidised:

2Br -2e —> Brig)

Bromine is reactive and would react with.an anode that was not inert.
Bromine does not react with either carbon or platinum. The overall reaction
for the electrolysis is:
Pb?*,y + 2Brq —> Poy + Brig)

Corrosion and its prevention

Corrosion of a metal is the surface chemical reaction on the
metal by the action of air, water or other chemicals.

Corrosion of metals is caused by the action of air, water and other chemicals,
such as acids, on the metal surface. The very reactive alkali metals have to be
stored under paraffin to prevent corrosion occurring. The paraffin excludes the
corroding agents.

When calcium, which is also a reactive metal, is exposed to air, it tarnishes

rapidly due to oxide formation. The oxide formed flakes off easily, exposing
more of the metal to reaction with the oxygen in the air. Unlike calcium,
the oxide coatings formed by aluminium, nickel and zinc do not flake off
easily, so these metals are protected from further corrosion. The corrosion of
iron or steel results in the formation of hydrated iron(III) oxide (rust), which
does not protect the metal from further corrosion.

If a drop of water is placed on a piece of clean steel, an electrochemical cell

is formed with a cathode and an anode. The cathode and anode regions
differ in composition. The anode gets eaten away as the iron is oxidised:
Fei CGS 2+ ee ntnee =

At the cathode, the dissolved oxygen in the water reacts as follows:

HO, + 220 (a9) +2e > 20H (aq)
 OPTION2 ®t

The Fe** and OH™ ions diffuse away from the electrodes and form a
precipitate of iron(II) hydroxide:
Wey sg tae OU yaaa aU)ara
This is then oxidised by dissolved oxygen to form rust, Fe,O,.xH,O, where
x is variable.

Acceleration of corrosion oe
Px presence Si salt in water, which is likely near ie sea, Of in winter hs
deicing salts are used on roads, accelerates corrosion of iron and steel. This
is because it increases the conductivity of the electrochemical cell solution.
If iron is in contact with a metal such as lead, which is below it in the
electrochemical series, as for example when lead piping is joined to an iron
storage tank, the rate of corrosion is accelerated greatly.

Prevention ofcorrosion
Corrosion of iron and steel may be prevented or eerded by eatin to
exclude air or coating with tin, plastic, grease or oil. The protection against
rust afforded by these methods lasts only until the coating is scratched.
Galvanising, which involves coating the metal with zinc, affords protection
even after scratching. Since zinc is above iron in the electrochemical series,
it rather than the iron reacts, forming ions which go into solution:
2+
21.) —> Zn (aq)

The zinc corrodes and the iron is protected. This is a type of cathodic
protection, where the cathode is protected and the anode is eaten away.

If a sacrificial anode made from a more reactive metal such as magnesium

or zinc is connected to steel, the steel is protected. This method is widely
used to protect the steel of ships and underground or submerged oil
pipelines and water pipes. The anode is eaten away and the steel, which is
the cathode, is protected.

Other ways of preventing corrosion include alloying steel with a metal such
as chromium, which forms a more stable oxide coating.
»

Extraction of sodium - the Downs cell

The electrolyte is a molten mixture of sodium chloride and calcium
chloride. The calcium chloride is added to reduce the melting point of the
mixture to more economical levels. Inert carbon anodes are used because the
reactive gas chlorine is formed at the anode during the electrolysis. The
steel gauze, which separates the two electrode compartments, prevents the
sodium formed at the cathode from reaction with this chlorine.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Sodium Chlorine
chloride

Vs Sodium

Circular steel
cathode

Graphite Molten
anode @ sodium chloride

Fig. 24.2 The Downs cells

At the cathode, the reaction is:

Na‘
a
+ &= — x Nay

The molten sodium formed floats on the electrolyte and is removed using
the collecting pipe. The anode reaction is:

i.e. producing chlorine gas.

Uses ofsodium : ~
Soaiteng is the most widely used of the alkali metals. Sodium vapour is used
in street lighting. Sodium, alloyed with potassium, is used as a coolant iin
some nuclear reactors.

Extraction of aluminium from bauxite

Crushed praiee is eet with mixing, to a hot Slecon of sodium
hydroxide. The following reaction occurs, in which soluble sodium
aluminate is formed:
2NaOH(4)+ Al,O3.3H,0 > 2ZNAAIO,/49) + 4H Oy
The impurities in the ore, which are mainly oxides of iron, silicon and
titanium, do not dissolve and are allowed to settle before being removed by
filtration.
ae yeu OPTION2
The clear sodium aluminate solution is next pumped to precipitator tanks.
Here the solution is seeded with very pure small crystals of aluminium
oxide-3-water. On cooling, the following reaction occurs:

2NaAIO...4) + 4H 0% > 2NaOH:,.) + Al,O3.3H,0.)

The precipitate of hydrated aluminium oxide is removed by vacuum
filtration, while the sodium hydroxide solution is recycled to the start of the
process. The hydrated aluminium oxide is then heated at about 1373 K to
remove the water of crystallisation:

Al,05.3H,0,4 > Al,Oaq + 3H,Op

The alumina formed is a white powder.

Aluminium from alumina

The electrolysis of alumina is carried out in large steel boxes lined with
carbon. The electrolyte used is a mixture of molten cryolite (Na,AIF,) and
aluminium fluoride (AIF; ). The aluminium oxide dissolves in the
electrolyte.

A low voltage is used in the electrolysis to avoid decomposing the

electrolyte. Large amounts of electricity are required for the electrolysis.
During the electrolysis, the following reactions occur:

Cathode: 2AI?* Sn6e > 2A\\

Anode: 307" 6e- > 1204)

Graphite anodes
Solid crust
of electrolyte

Graphite
lining acting
as cathode

Insulator

Molten Aluminium oxide

aluminium dissolved in molten cryolite

Fig. 24.3 The electrolysis of alumina

The electrolysis is carried out at a high temperature, at which the large

carbon anodes are steadily burnt away by the oxygen liberated there and
have to be replaced at regular intervals.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Alumina has a very high melting point (2288 K). The reason cryolite is
used as a solvent in the electrolysis is that it has a much lower melting point
than alumina itself. The electrolysis of alumina consumes enormous
amounts of electricity and is therefore normally carried out where electricity
is relatively cheap.

The extraction of aluminium oxide from bauxite results in the formation of

very large amounts of red mud, which is unsightly.

Aluminium is used to make strong, light, corrosion-resistant alloys, which

are used in the construction of aeroplanes and ships. Aluminium is a good
conductor of heat and so is used to make saucepans and as cooking foil. It
is an excellent electrical conductor and so is used in electricity wires.

Anodising
The natural coating of aluminium oxide, which forms on the surface of
aluminium as soon as the metal is exposed to thé air, can be thickened by an
electrolytic process called anodising. The purpose of anodising is to produce
a very hard coating or one that is very resistant to-corrosion. In anodising,
the aluminium is used as an anode in the electrolysis of dilute sulfuric acid.
Graphite, platinum or another inert cathode can be used. The electrolysis of
the dilute acid results in the formation of oxygen at the anode:

H, Oy) = 2H" aq) = 2204) + 2e-

This reacts with the aluminium anode forming a tenacious coating of

aluminium oxide on the surface of the metal. The cathode reaction is:
x a
2H ee 2e => Hog)

The anodised aluminium is porous. This allows it to be dyed easily. The

anodised aluminium used in aluminium windows and doors is often dyed.

Recycling of aluminium
The recycling of aluminium is an economically viable process. It is also
desirable from an environmental point of view. When aluminium is being
recycled, the aluminium waste is melted. The impurities are either burned
off or separated from the aluminium.

Transition metals

Transition metals have variable valencies, form coloured compounds

and they and their compounds have catalytic properties.
 OPTION 2
Iron and copper are transition elements:
1 They form coloured compounds, such as iron(II) sulfate-7-water,
which is green, and copper(II) sulfate-5-water, which is blue.
2 They have a number of different oxidation states (variable valencies) —
iron in its compounds usually has an oxidation state of +2 or +3, while
copper in its compounds usually has an oxidation state of +2 or +1.
3 They have catalytic activity — for example, an iron catalyst is used in
the Haber process for the synthesis of ammonia, while finely divided
copper is used in the industrial synthesis of methanal.

Manufacture of iron and steel

Iron occurs naturally in ores such as haematite (impure Fe,O,), magnetite
(impure Fe,O,) and iron pyrites (impure FeS).

Manvfacture of iron
The raw materials for the blast furnace process for the extraction of iron
from ores such as haematite are: coke, limestone and the ore itself. In the
blast furnace process, the ore, coke and limestone are fed regularly into the
furnace from the top. Coke is mainly composed of carbon and the ore is
reduced by reaction with carbon:

Fe,03,. + 3C,) > 2Fe.) + 3CO(,)

The carbon monoxide causes further reduction in the upper, cooler regions
of the furnace:
Fe, Ox + 3COq > 2Fe + 3COx6
Most of the reduction of the iron ore is caused by carbon monoxide. The
gases formed (CO, CO,) are drawn off through ducts. The limestone
decomposes into calcium oxide and carbon dioxide. The calcium oxide
reacts with impurities in the iron ore, forming slag:
CaO + SiO, > CaSiO,
CaO + Al,O; > CaAl,O,

The molten iron and slag trickle down into the hearth, where the less dense
slag floats on the iron. The slag and iron are separately tapped off into large
tanks. At this stage, the iron is not very pure and, if allowed to solidify,
forms pig iron.
PP )__LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Charge of iron ore, Gas outlet

coke and limestone |

Brick lining

Hot air

Slag outlet
Molten slag

Molten iron

lron outlet

Fig. 24.4 The blast furnace

The slag is used in road making.

Manvfacture of steel ,
To make steel from iron, the iron must first be purified. Oxygen is blown
onto the surface of the liquid iron at the base of the furnace. This-oxidises
silicon, manganese and some iron and the products are removed as slag.
Carbon is also oxidised and the gaseous products escape to the atmosphere.
The molten iron, which is now sufficiently pure, is poured into a ladle and
carefully measured amounts of carbon and other elements are added. This
process is called the basic oxygen process. ;

Properties of different steels

Alloying carbon with iron to make steel increases the hardness and strength
of the metal. Other metals may be added in controlled amounts as well. By
a correct choice of metal, and proportion of this metal added to iron, steels
can be made which are very hard or very resistant to corrosion or of great
strength. Metals such as tungsten are used to harden steel. Corrosion-
resistant steels are made using chromium and nickel. Manganese is used to
make very tough steel.
 OPTION? OBER
Uses of in
iron andsee
Sree is Reed in ine Eranulercnure of car bodies and in ate construction fo
bridges and buildings. The uses of iron are more limited. It is used, for
example, in manhole covers, chains and gates.

Electric arc process for steel! manufacture

Steel is made from recycled steel, which is melted in an electric arc furnace
before it is refined and cast and rolled into steel products.

1 Charging
Ab overhead crane
< is used to add he scrap to oie furnace, linge (lin
oxide) is added to absorb the acidic impurities during the melting and
refining stages and to form slag.

2 Melting
An electric arc is ak ea carbon leas eal ae Crap. rife
generates very high temperatures, melting the steel quickly.

5 Refining CHRTER OTH SE VEDA

oo is Blewn onto oe molien sreclettooie non-waste lands to

their oxides. Excess carbon burns to form carbon monoxide and carbon
dioxide:
Es Ox) 25 OG
200.) a Oo) = 2CO5¢g)

Non-metals present, such as silicon, will form oxides which then react with
lime to form calcium silicate, a component of slag:

Slit) One SIO;

Gala SiOx CasiO,
Phosphorus and aluminium oxides are removed in a similar manner.

Slag is less dense than liquid stecl and floats on top, which means that it
can be easily removed. Tilting the furnace pours off the liquid slag.

4Tapping |
fine liquid seas is next feeed Hoa Ane fienace into an enleaed oe
The composition of the steel is adjusted by adding the required amounts of
alloying elements.
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

COCR TEHOH OD

The aiken steel is then poured into a casting machine where a slab of solid
steel is formed.

Environmental aspects of iron and steel production

If iron is being extracted from a sulfide ore, some sulfur dioxide will be
formed in the blast furnace. When coke is being produced from coal, for use
in the blast furnace, smoke and sulfur dioxide are formed. Emissions of
these must be kept to a minimum. Fumes from a blast furnace must also be
cleared of dust particles before being released into the atmosphere.

All emissions from the steelmaking plant have to be carefully monitored.

Fumes are filtered to remove dust particles and water used for cooling
purposes is recycled. The use of natural gas for heating eliminates emissions
of sulfur dioxide, which can be a problem if oil or coal is used instead.
_—

A crystal is a solid in which the atoms, ions or molecules of which it *

iS composed. ‘are arranged in a regular three-dimensional structure.
See Table 24.1 for summary of different types of crystal.
_ See Table 24.2 for summary of properties of different types of crystal.
A polymer ts a large molecule made up of many identical repeating units
called monomers.
- See Table 24. 4 for the physical properties of metals and non-metals.
An aus isa mixture of two or more elements, at least one of which is a
metal. > he a
Corrosion of a metal is the surface chemical reaction on the nae by the
action of air, water or other chemicals. «
Transition metals have variable valencies, form coloured compounds, and
_ they and their compounds have catalytic properties. ;

Your revision notes

 Questions from the 2008
Examination

Sample Questions
2008, Hl, Section A, Question 1
terest

3 iderenrine the BORIS of ethanoic “acd: CH.,COOH, inaa one of

vinegar, the vinegar was first diluted and then titrated against 25.0 cm?
portions of a previously standardised 0.10 M solution of sodium hydroxide,
NaOH. One rough and two accurate titrations were carried out.

The three titration figures recorded were 22.9, 22.6 and 22.7 cm?, respectively.
(a) Why was the vinegar diluted? a (5)
(b) Describe the correct procedures for measuring exactly 25.0 cm3 oo
vinegar and diluting it to exactly 250 cm? using deionised water. (15)
(c) The equation for the titration reaction is:

‘CH,;COOH + NaOH -> CH,COONa+H,O —

Name an indicator suitable for this titration. Justify your choice of
indicator. © / A
State the colour change at the end paint, s Pie eee Pats
Calculate the concentration of the diluted solution of ethanoic |
acid in (i) moles per litre, (ii) grams per litre.
State the concentration of ethanoic acid in the original vinegar sample
in grams per litre. Express this concentration in terms of % (w/v). (15)
fe) Ethanoic acid is a carboxylic acid. Identify the carboxylic acid
apes which occurs in nettles and stinging ants. (3)

2008, Ht, Section 6, Question 6

2 (a). ce hydrocarbon ‘molecules in petrol Peay ee carbon chains
with between five and ten carbon atoms. The most widely used
petrol in Ireland has an octane number of 95.
ues (i) What is meant by the octane number of a fuel?
oo (ii) The two hydrocarbons used as references when establishing
the octane number of a fuel are heptane and 2,2,4-
_trimethylpentane. Draw the structure of each of these
molecules. —
(continued)
LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

Crude oil is separated into a number of fractions in oil refining.

Name the two fractions which contain molecules with the
carbon chain lengths needed for petrol.
Dehydrocyclisation is one of the processes used to increase
the octane numbers of hydrocarbons.
What two changes to the hydrocarbon molecules occur
during this process?
Ethanol is an example of an oxygenate. Give ana
example of an oxygenate.
Give two reasons why oxygenates are added to petrol.

Write a balanced chemical equation for the combustion of ethanol,

C,H,OH.
eae that the heats of formation of ethanol, carbon dioxide
and water are -278, -394 and -286 kJ mol", respectively,
calculate the heat of combustion of ethanol. .

2008, Hb, Section B, Question ) t

The alkenes.are a Roroloncue series of unsaturated hydrocarbons. Ethene
(C,H,) is the first member of the series. Alkenes undergo addition reactions
and polymerisation reactions.
(a) Draw a labelled diagram of an apparatus used to prepare ethene
gas in the school laboratory. (8)
(b) Draw the structure of any one of the isomers of the third member
of the alkene series. Indicate clearly which carbon atoms have
planar bonding and which are bonded Ueda (12)
Explain the term unsaturated. (6)
The ionic addition mechanism for the reaction of ethene with
bromine water involves the formation of an intermediate ionic
species. Draw the structure of this species.
Give the names or structural formulas of the three products
that would be formed if the bromine water used in the reaction
contained sodium chloride.
How does the formation of these three products are the
mechanism of ionic addition?
Name the polymer formed when ethene undergoes addition
polymerisation.
Draw two repeating units of this polymer.
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 LEAVING CERTIFICATE CHEMISTRY — HIGHER LEVEL

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 A
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