THE OPEN UNIVERSITY OF TANZANIA

Institute of Continuing Education

FOUNDATION PROGRAMME

OFP 016
CHEMISTRY
Published by:
The Open University of Tanzania
Kawawa Road,
P. O. Box 23409,
Dar es Salaam,
TANZANIA.
www.out.ac.tz

First Edition: 2013

Second Edition: 2018
Copyright © 2013
All Rights Reserved

ISBN 978 9987 00 253 5

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Contents

GENERAL INTRODUCTION ................................................................................................ 7

SECTION 1: FUNDAMENTAL CONCEPTS

Lecture 1: Some Fundamental Concepts ................................................................................. 8
1.1 Introduction ............................................................................................................. 8
1.2 Scientific Method .................................................................................................... 9
1.3 Some Basic Definitions...........................................................................................10
1.4 Units of Measurements ...........................................................................................14
1.5 The Atomic Theory ................................................................................................15
1.6 Chemical Bonding ..................................................................................................16
1.7 Chemical Change....................................................................................................19

Lecture 2: The Mole Concept..................................................................................................23

2.1 Introduction ............................................................................................................23
2.2 Atomic Mass ..........................................................................................................23
2.3 The Mole ................................................................................................................24
2.4 Molar Mass (Molecular Weight) .............................................................................25
2.5 Percentage Composition by Mass............................................................................26
2.6 Combustion Analysis ..............................................................................................26
2.7 Reaction Yield ........................................................................................................28

SECTION 2: ATOMIC STRUCTURE AND THE PERIODIC TABLE

Lecture 3: Atomic Structure ...................................................................................................35
3.1 Introduction ............................................................................................................35
3.2 What is an Atom? ...................................................................................................35
3.3 Relationship of Atomic Particles .............................................................................37
3.4 Discovery and Arrangement of Subatomic Particles in the Atom .............................39

Lecture 4: The Periodic Table of Elements ............................................................................44

4.1 Introduction ............................................................................................................44
4.2 The Periodic Table of Elements ..............................................................................44
4.3 Electron Configuration of Atoms (ee) .....................................................................45
4.4 Quantum Numbers and the Periodic Table ..............................................................50
4.5 Periodic Variation in Physical Properties ................................................................51

SECTION 3: GASES
Lecture 5: Properties of Gases ................................................................................................56
5.1 Introduction ............................................................................................................56
5.2 Definition of Gas ....................................................................................................56

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 5.3 Properties of Gases .................................................................................................57

Lecture 6: Gas Laws................................................................................................................61

6.1 Introduction ............................................................................................................61
6.2 The Pressure-Volume Relationship: Boyle’s Law ...................................................61
6.3 The Temperature-Volume Relationship: Charles’ and Gay-Lussa’s Laws ................62
6.4 The Volume-Amount Relationship: Avogadro’s Law ..............................................65
6.5 The Ideal Gas Law..................................................................................................66
6.6 Gas Mixtures ..........................................................................................................68

SECTION 4: INORGANIC CHEMISTRY

Lecture 7: Qualitative Inorganic Analysis ..............................................................................72
7.1 Introduction ............................................................................................................72
7.2 Analysis of Anions .................................................................................................72
7.3 Analysis of Cations .................................................................................................82
7.4 Separation of Individual Ions ..................................................................................86
7.5 Dissolution of Precipitates to form Complex Ions ...................................................89
7.6 Confirmation Test for Ions ......................................................................................89

Lecture 8: Acids and Bases .....................................................................................................93

8.1 Introduction ............................................................................................................93
8.2 Definitions of Acids ................................................................................................93
8.3 Theories of Acids and Bases ...................................................................................94
8.4 Basicity ..................................................................................................................98

Lecture 9: Solutions of Acids and Bases ............................................................................... 101

9.1 Introduction .......................................................................................................... 101
9.2 Aqueous Solutions of Acids and Bases ................................................................. 101
9.3 pH ........................................................................................................................ 103
9.4 Bronstead Acids and Bases ................................................................................... 107
9.5 The Hydronium Ion (H3O+) ................................................................................... 108
9.6 Strong Acids and Weak Acids............................................................................... 109
9.7 The Carbonate System .......................................................................................... 111

SECTION 5: INTRODUCING THE HYDROCARBONS

Lecture 10: Alkanes............................................................................................................... 114
10.1 Introduction .................................................................................................. 114
10.2 Definition of Alkanes ................................................................................... 114
10.3 Nomenclature of Alkanes.............................................................................. 115
10.4 Physical Properties of Alkanes ...................................................................... 118
10.5 Reactions of Alkanes .................................................................................... 118
10.6 General Methods of Preparation of Alkanes .................................................. 120

Lecture 11: Cycloalkanes ...................................................................................................... 122

11.1 Introduction .................................................................................................. 122

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 11.2 Definition of Cycloalkanes ........................................................................... 122
11.3 Phyisical Properties of Cycloalakanes ........................................................... 123
11.4 Chemical Reactivity of Cycloalakanes .......................................................... 124

Lecture 12: Alkenes ............................................................................................................... 126

12.1 Introduction .................................................................................................. 126
12.2 Definition of Alkenes ................................................................................... 126
12.3 Nomenclature of Alkenes.............................................................................. 127
12.4 Properties of Alkenes .................................................................................... 128
12.5 Reactions of Alkenes .................................................................................... 129
12.6 General Methods of Preparation of Alkenes .................................................. 140

SECTION 6: INTRODUCING OTHER ORGANIC COMPOUNDS

Lecture 13: Halogenoalkanes (Haloalkanes) ........................................................................ 144
13.1 Introduction .................................................................................................. 144
13.2 Definition of Halogenoalkanes ...................................................................... 144
13.3 Physical Properties of Halogenoalkanes ........................................................ 146
13.4 Chemical Reactivity of Halogenoalkanes ...................................................... 148
13.5 Reactions of Halogenoalkanes ...................................................................... 149
13.6 Preparation of Grignard Reagent from Halogenoalkanes ............................... 150
13.7 Reactions of Grignard Reagent ..................................................................... 151

Lecture 14: Aryl Halides ....................................................................................................... 156

14.2 Definition of Aryl Halides ............................................................................ 156
14.3 Structure of Chlorobenzene........................................................................... 156
14.4 Phyisical Properties of Aryl Halides .............................................................. 157

Lecture 15: Alcohol ............................................................................................................... 159

15.1 Introduction .................................................................................................. 159
15.2 Definition of Alcohols .................................................................................. 159
15.3 Classification of Alcohols ............................................................................. 160
15.4 Phyiscal Properties of Alcohols..................................................................... 161
15.5 Manufacture of Alcohols .............................................................................. 164
15.6 Making Ethanol by Fermentation .................................................................. 166
15.7 Reactions of Alcohols ................................................................................... 167
15.8 Esterification of Alcohols ............................................................................. 177

Lecture 16: Carbonyl Compounds........................................................................................ 182

16.1 Introduction .................................................................................................. 182
16.2 Definition of Carbonyl Compounds .............................................................. 182
16.3 Reactivity of Carbonyl Compounds .............................................................. 184
16.4 Phyisical Properties of Carbonyl Compounds ................................................ 184
16.5 Making Aldehydes and Ketones .................................................................... 186
16.6 Reduction of Aldehydes and Ketones ............................................................ 188
16.7 Reaction of Carbonyl Compounds with Grignard Reagent............................. 191

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Lecture 17: Carboxylic Acids ................................................................................................ 195
17.1 Introduction .................................................................................................. 195
17.2 Definition of Carboxylic Acids ..................................................................... 195
17.3 Physical Properties of Carboxylic Acids ....................................................... 196
17.4 Making Carboxylic Acids ............................................................................. 197
17.5 Carboxylic Acids as Acids ............................................................................ 199
17.6 Reactions of Carboxylic Acids ...................................................................... 200
17.7 Esterification of Carboxylic Acids ................................................................ 202

THE PERIODIC TABLE OF ELEMENTS ......................................................................... 214

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General Introduction
Course Description
Chemistry is the central science that impacts on all aspects of our lives. An understanding of
chemistry is necessary to all other sciences, from astronomy to zoology. All of the materials used
by engineers and technologists are made by chemical reactions, and we all experience chemical
reactions continuously in our lives, whether it be breathing or baking a cake. Chemistry is
concerned with all aspects of molecules, their physical and chemical properties, their composition
and structure, their synthesis and use.
This course is designed to prepare students intending to pursue Chemistry and other natural
sciences courses in their degree programmes. It is organized in seventeen lectures that are grouped
into six sections. It offers a conceptual approach to Chemistry by first revising the fundamental
chemistry concepts such as matter and its properties, the atomic theory, chemical bonding,
chemical formulas, chemical reactions, gases, liquids, solutions, and solving stoichiometric
problems. It then covers topics in qualitative inorganic chemistry, including acids and bases,
analysis of cations and anions, and formation of complex ions. Finally it introduces organic
chemistry, including nature, structure and properties of different types of organic compounds.
Students who will go through this course successfully will be in a good position to take Chemistry
courses in their bachelor degree programmes.

Course Objectives:
It is expected that by the end of this course students will be able to:
1. Apply fundamental concepts of Chemistry such as matter and its properties, chemical bonding,
chemical reactivity, molecular structure and solution chemistry in science, technology and related
disciplines.
2. Describe the atomic structure and properties of different elements as provided in the Periodic
Table of Elements
3. Apply gas laws to perform calculations related to gas properties.
4. Apply fundamental principles of inorganic chemistry to perform qualitative and quantitative
analysis of chemicals
5. Describe the hydrocarbons, including their nomenclature, properties and reactions
6. Identify functional groups of different organic chemicals, their nomenclature, properties,
preparations and reactions of different types of organic compounds.

Pre-requisite
To be able to do this course students must have studied Chemistry at the
Ordinary Level of Secondary Education.

Mode of Assessment
Continuous Assessment: 30%
Annual Examination: 70%

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Lecture 1
Some Fundamental Concepts

1.1 Introduction
The introductory lecture discusses the scope, objectives, and methods of chemistry. It also introduces
some of the basic vocabulary and notations that will be used in the remainder of the lecture. Classification
of matter and technologies for separating mixtures will also be discussed. Elementary atomic theory is
presented from an experimental perspective and related to the periodic table.

Learning Objectives
At the end of this lecture, you will be able to:

 Define chemistry
 Outline the scientific method
 Classify material properties
 Tell how chemical changes differ from physical changes
 Distinguish between the three states of matter
 Relate the names of elements to their international element symbols and tell why some elements
symbols are unrelated to the name
Now let us begin our lecture by recalling the definition of Chemistry.

Definition of Chemistry
In the literature, you will encounter various definitions. However, in essence all are saying the same thing.
Two versions are presented below:

1. Chemistry is the study of matter and its transformations. It is the study of connections between
molecular and macroscopic events.

2. Chemistry is the science in which substances are examined to find out what they are made of,
how they act under different conditions, and how they are combined or separated to/from other
substances.

In other words, Chemistry deals with finding what different substances are made of, what kind of
transformations take place, and different chemically related facts about a certain organism or substance.

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 ? Activity 1.1
What can you say about the above two definitions?

1.2 Scientific Method

In all sciences, there is a system that describes how to go about solving problems. This system is called
the Scientific Method. Basically, there are four parts to this system that are very logical in order.

(a) An observation must be made. Observations can be either in the form of quantitative observations
or qualitative observations. Quantitative observations have to do with numbers, whereas
qualitative observations have to do with a physical characteristic of something. For example, the
observer observes a two winged red butterfly. The fact that the butterfly has two wings is a
quantitative observation and the fact that the wings are red is a qualitative observation.

(b) After making many observations, the observer formulates a question, which is normally, why did
that happen?

(c) The observer looks for possible reasons, that is formulates theories. A theory is the observer's
interpretation of the data collected. The first set of theories is called a hypothesis. A hypothesis is
simply an educated guess on the part of the observer to explain the question at hand.

(d) The observer tests his theory by experimentation. If the theory is wrong the observer goes back
and formulates a new theory, and if the theory is right, the observer goes back and retests it.

Science is in no way perfect. People do make mistakes, this is part of the human nature, but as technology
improves and more people test the previous theories, the wrong ones get sorted out from the right ones
and science corrects itself.

Schematically we can represent the scientific method (See Figure 1.1).

For chemistry (as shown in Figure 1.1) is best looked at as follows:

 Observations refer to measurement in the macroscopic world – using balances, rulers, beakers,
burettes, pipettes and so forth.
 Representation involves the use of special symbolic and equations for communication.
 Interpretations are based on atoms and molecules, which belong to the microscopic world.

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 Observation

Hypothesis

Theory

Theory modified
as necessary

Theory tested by
further experiments

Figure 1.1: The Scientific Method

It is this notion of switching between two worlds, which create problems to some people when they learn
chemistry for the first time.

1.3 Some Basic Definitions

Some words which are used in everyday conversations have different meanings when used in scientific
language. In this lecture we will give definitions of important and fundamental terms that have direct
application to nearly all what we will discuss in this lecture and in further study in chemistry.

1.3.1 Matter

Matter is anything that has mass and occupies space. In simpler terms, matter consists of some "thing"
with volume. It is essentially anything you can directly or indirectly touch, see, feel, taste, or smell.

Activity 1.2
? Give five examples of matter which you can think of

Did your answer compare in any way like the one given below?

"Matter is the stuff around you"

Anything that takes up space or has a mass of any kind is matter. Everything you can touch is made of
matter. If it is made of anything, that anything is matter. Everything you will learn about Chemistry will all
be based on how matter reacts and combines, such as: table, clouds, water, air, ugali, yourself, etc.

Matter has properties, which help to distinguish one matter from the other. A property is any characteristic
that can be used to describe or identify something. Properties can be either physical or chemical.

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1.3.2 Mass and Weight

Mass is a measure of the quantity of matter and weight is a measure of force. On earth, weight is the
measure of attraction between the earth and the mass in question. Before the exploration to the moon or
space it was 'normal' to use mass and weight interchangeably: This was acceptable because we were
referring to the pull of gravity on the earth's surface.

The weight of John Young on the moon was one sixth that on earth because the moon's pull is only one
sixth as strong as the earths. On a different note, the mass of an object can be determined readily with a
balance, and this process, oddly, is called weighing. Hence, this is partly the reason why we use mass and
weight interchangeably.

Take Note
Weight varies with gravity; mass does not.

1.3.3 Substances and Mixtures

There are three main states of matter: Solids, Liquids and Gases. Solids ordinarily maintain their shape and
volume regardless of their location. A liquid occupies a definite volume, but assumes the shape of the
occupied portion of the container. This property of definite volume of liquids is used so much in chemistry
of transferring samples using pipettes, burettes or measuring cylinders. Gases maintain neither shape nor
volume. They expand to fill completely whatever container one puts them in. Gases can be easily
compressed.

Classification of Matter: Matter can be classified in yet another way – that is, it can be divided into two
broad classes: mixtures and pure substances.

A pure substance is a form of matter that has a definite or constant composition (the number and type of
basic units present) and distinct properties. Pure substances differ from one another in composition and
can be identified by their appearance, smell, taste, and other properties.

A mixture is a combination of two or more substances in which the substances retain their identity.
Mixtures are a physical or mechanical combination. A combination can be uniform and homogeneous
like homogenized milk or it can be heterogeneous (the individual components remain physically separated
and can be seen as separate components) like sugar and sand. Shaking mixes the oil and water into
assorted sized globs. The mixture separates when allowed to stand. Gravity physically pulls the denser
water layer down under the lighter less dense oil.

Mixture  pure substances

physical change

The following is a diagrammatic representation of the classification of matter.

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 Matter

Heterogenous Physical methods Homogenous

mixtures mixtures
Physical methods
Pure Substances

Compounds Chemical methods Elements

Atoms

Nucleus Electrons

Protons Neutrons

Figure 1.2: Classification of Matter

Mixtures can be made in any proportions. Salt water can be a litre of water with a few grams of salt. Salt
water can also be a saturated solution of a litre of water and more than 400 grams of salt. The particles
retain their identities and the original substances can be recovered using physical process. Sand and iron
filings can be mixed. The iron can be removed using a strong magnet.

Water is always H2O. Table salt is always NaCl.

When you make salt water the mixture is mechanical. The particles in the mixture will still be H 2O and
the particles from NaCl will be Na+ and Cl–.

1.3.4 Chemical and Physical Properties

Physical Properties: Physical properties are solubility, volume, length, colour, odour, melting point, and
boiling point. The physical properties are measured or observed without changing the identity of the
substance or matter in the object. When sugar dissolves in water the sugar particles (molecules) are simply
separated from one another. The water molecules surround the sugar particles. The sugar and water retain
their individual structure. If you boil off the water, the sugar can be recovered. Mechanical physical
changes are reversible. One physical change can undo another.

Chemical Properties: Chemical properties are observed when changes occur in the identity of the
matter in a substance. The colour changes in plant leaves and flowers result from chemical reactions. The
burning of hydrogen gas in oxygen to form water is a chemical property of hydrogen.

. Take Note You must have noticed that if you throw iron nails in open air and leave them
exposed to the air, rain, and sun, the nails will slowly react with the oxygen and water to form a new
brown substance. The colour will change from the grey colour to the brown of corroded Iron, Iron III
oxide. This interaction between Iron metal, water and oxygen is a chemical property.

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When gold is exposed to the same conditions as those described for iron, nothing happens to the colour.
The gold, water and oxygen do not interact. You can say that one chemical property of gold is that it does
not react with oxygen. Because gold is relatively not reactive it retains its lustre, this property makes it
useful in jewellery.

1.3.5 Atoms and Molecules

Atoms: All matter is composed of atoms of different kinds, combined in many different ways. Atoms are
the smallest possible units of a substance. Atoms are the basis of chemistry. They are the basis for
everything in the Universe. Every basic atom has three particles. These are electrons, protons, and
neutrons. In this lecture we are going to cover basics like atomic structure and bonding between atoms.

Molecules: Molecules are made up of atoms held together by Special Forces = bonds.

1.3.6 Elements and Compounds

Substances can be either elements or compounds. An element is a substance that cannot be separated into
simpler substances by chemical means. There are about 109 known elements. Elements play as central a
role in chemistry as, for example, letters of the alphabet play in the study of language. Because of this
importance, chemists have devised several related ways of tabulating information regarding the known
elements.

A compound is a substance composed of atoms of two or more elements chemically united in fixed
proportions. Compounds have properties that are distinctly different from those of the starting atoms.
Compounds are represented using formulas. These use the element symbols and subscripts. The element
symbols tell what kind of atoms are in the compound. The subscripts tell the number of each type of
atom.

Let us elaborate more on chemical elements. As mentioned above that there are more than 109 known
elements. The original alchemists found it convenient to use an abbreviation to represent an element. The
modern element symbols are usually based on the element names. The symbol starts with a capital letter.
The symbols for the elements are often the first letter in the element name or the first and second or third
letter. The same set of symbols in referring to chemicals is used universally. The symbols are written in
Roman letters regardless of language. Usually the metallic elements have a name ending in -ium. Like any
generalization, there are clear exceptions like helium, He. Look at the following examples to see how the
symbols and names relate.

Modern names Latin names

bismuth is Bi lithium is Li platinum is Pt tin Sn (stannum)
boron is B magnesium is Mg radon is Rn potassium K (kalium)
calcium is Ca manganese is Mn silicon is Si silver Ag (argentum)
carbon is C nickel is Ni sulfur is S sodium Na (natrium)
chlorine is Cl helium is He zinc is Zn Copper Cu (cuprum)

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One column in the table above is labelled as Latin names; these are some elements, which have retained
their ancient names, which were in Latin.

1.4 Units of Measurements

In science and chemistry, measurements are very important. Measurements are quantitative observations.
A world-wide system of measuring is the Metric System, or SI system. This system is based on multiples
of ten as shown in the Table 1.1. For example, if you have 1 meter, you have 100 centimetres, 1000
millimetres, and .001 kilometres. This is obviously easier to understand (see table 1.1).

SI system base units for measurement:

 Meter for length,
 Litre for volume, and
 Gram for mass

Table 1.1: Commonly Used SI Prefixes

Prefix Symbol Meaning Exponential

Notation
mega M 1,000,000 106
kilo k 1,000 103
hector h 100 102
deka da 10 101
----- ----- 1 100
deci d .1 10-1
centi c .01 10-2
milli m .001 10-3
micro µ .000001 10-6
The prefixes shown in table 1.1 above are standard for all the base units. So if you have a kilogram of
water, you have 1000 grams of water and if you have a kilometre of road, you have 1000 meters of road.

It is important to understand that in science, when you take measurements the last number is always
estimated. For example, if the ruler you were using to measure a piece of paper was calibrated to
centimetres (meaning the smallest marked units were centimetres) and the length came out to 20
centimetres, this answer would not be acceptable because the answer has to have an uncertain value
which would be the millimetre’s value.

Take Note
Measurements must always be one decimal place more exact than the smallest marked units on the measuring device

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1.5 The Atomic Theory
The microscopic composition of matter that is the symbolic representations; chemical formulas and
nomenclatures employed by chemists provide convenient ways of communicating detailed knowledge of
the makeup of chemical substances.

1.5.1 Daltons Atomic Theory

Summary of Daltons atomic theory is described below:

 Elements are composed of extremely small particles, called atoms.

 All atoms of a given element are identical, having the same size, shape, mass, and chemical
properties. The atoms of one element differ from the atoms of other elements.

 Chemical compounds are composed of atoms of more than one element. In any compound, the
ratio of the numbers of atoms of any two of the elements present is either an integer or a simple
fraction.

 A chemical reaction involves only the reorganisation (separation, combination, or rearrangement

of atoms) it does not result in their creation or destruction.

The last hypothesis is another way of stating the Law of conservation of mass.

Activity 1.3
? State the law of conservation of mass.

1.5.2 Chemical Formulas

In section 1.4.5 we gave definitions of atoms and molecules. Now, employing the Daltons Atomic
Theory, we are in a position to give another version of definitions as follows: An atom is the basic unit of
an element that can enter into chemical combination, and a molecule is an aggregate of at least two
atoms in a definite arrangement held together by special force – bonds.

An individual atom can be represented by the symbol of the element, with the charge and mass of the
atom indicated when appropriate. All compounds are composed of different elements and different
numbers of them. To identify which elements and how many of them are present in different
compounds, a set of rules were set up to identify compounds. The rules are very simple. The first rule is
that chemical symbol is written to tell what element is used in a compound and the second rule is a
subscript that follows the symbol to tell how many of these elements are present. The name of the
substance using this method of naming is called the molecular formula. An example of the molecular
formula are H2O (2 atoms of hydrogen and 1 atom of oxygen), CO2 (1 atom of carbon and 2 atoms of
oxygen), and Br2 (2 atoms of bromine). Empirical formulas give the correct relative atomic composition but
do not give the molecular formula (details on this will be encountered under polymers).

All formulas that are multiples of simpler ratios can be assumed to represent molecules: The formulas N 2,
H2, H2O2, and C2H6 represent nitrogen gas, hydrogen gas, hydrogen peroxide, and ethane. However,
formulas that show the simplest possible atomic ratios must be assumed to be empirical unless evidence

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exists to the contrary. The formulas NaCl and Fe2O3, for example, are empirical; the former represents
sodium chloride (table salt) and the latter iron oxide (rust), but no single molecules of NaCl or Fe 2O3 are
present.

When groups of atoms combine as a subunit, the subunit is usually treated as a single symbol. For
example, the sulfate group, SO42-, is treated as a single symbol (included in molecules such as Al2(SO4)3,
aluminum sulfate), as is the nitrate group, NO 3- (included in molecules such as NH4NO3, ammonium
nitrate).

There are still other ways of showing what atoms and how many are in compounds. Another way might
be to draw the structural formula. The structural formula is a picture that shows what atoms are bonded
to what atoms and what the relative positions of the atoms are in the compound. In this type of formula
lines are drawn between the atoms to show how atoms are bonded together.
H H H H

H C C O H H C O C H

H H H H

Ethyl alcohol Dimethyl ether

1.6 Chemical Bonding

Studying the chemical bond help us understand the forces that hold atoms together in molecules and ions
together in ionic compounds.

There are more than 100 chemical elements. There are millions of chemical compounds. To form these
compounds, atoms of different elements must be held together in specific combinations. Chemical
bonds are the forces that maintain these arrangements. Chemical bonding also plays a role in determining
the state of matter. At room temperature, water is a liquid, carbon dioxide is a gas, and table salt is a solid
– because of differences in chemical bonding.

1.6.1 Why are Chemical Bonds Formed?

Chemical bonds form to lower the energy of the system, the components of the system become more
stable through the formation of bonds. Everything wants to be more stable – it is easy to lie down than
stand up, bonding is Nature's way of allowing the elements to lie down.

If we examine the periodic table, we find that the elements in Group VIII (helium, neon, argon and so
on), are particularly stable, so much so that they were once labelled the "inert gases". We now know that
these elements are not inert. Indeed xenon forms a range of compounds, but, nevertheless, they are very
stable. Hence, now we refer to these elements as the noble gases. This stability is the result of their
electronic configuration, they have a full valence shell of electrons and this imparts stability. G. N. Lewis
(1916) suggested that bonds (covalent) formed to enable elements to attain this "noble gas configuration".
We can extend this idea to ionic compounds, in a compound such as sodium chloride, one element loses
electron(s) to gain this stable electronic configuration whilst the other gains electron(s) to achieve the
same result.

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 Take Note
We can see that in each case, sharing or transfer of electrons, results in a more stable system.

Can we predict the type of bonds, which will form between different elements in the periodic table?

The answer is usually yes. The elements to the left of the periodic table (Groups I
and II) can achieve the noble gas electronic configuration by losing electron(s). Ionization enthalpies
show that loss of electrons of these is relatively easy (ionization enthalpies are fairly low for the elements
in these groups). These elements are termed electropositive.

The opposite is true of the elements to the right of the periodic table. Elements in groups VI and VII can
most easily attain the noble gas configuration by gaining electron(s). These are the electronegative
elements. A measure of their ability to accept electrons can be seen in the electron affinity values for
these elements.

1.6.2 Types of Bonds and Properties of Resulting Compounds

Ionic Bonds
An ionic bond is the product of the electrostatic forces of attraction between positive (cations) and
negative (anions) ions. An ionic compound is a large collection of ions in which the positive and negative
charges are balanced. The structure of a solid ionic compound maximizes the net attractive forces among
the ions.

Properties of Ionic Compounds

Ionic compounds have the following properties:
 Ionic crystals consist of cations and anions arranged so that ions of opposite charge are as close as
possible in the crystal lattice.
 Ionic Crystals are transparent, hard, brittle, and can be cleaved along planes. This suggests that ions
are arranged in highly ordered patterns in the crystal lattice.
 Ionic compounds typically have high melting points and are solids at room temp. Melting point
correlates to some degree with the ionic charge. Ionic solids do not conduct electricity, but molten
salts do.
 Though pure water does not conduct an electric current, many ionic compounds dissolve in
water to form solutions that do conduct an electric current. They are called strong electrolytes.
 The high conductivity of aqueous solutions of ionic compounds suggests that the ions are mobile
when dissolved in water. Our model envisions water molecules surrounding (hydrating) the
individual ions to keep them separated.

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 Activity 1.4
(i) Name five metals and five non-metals, which are likely to form ionic compounds.
?
(ii) Write formulas for the compounds that might result from the combination of these metals and
non-metals. Name these compounds.

Covalent Bonds
In covalent bonding, both atoms are trying to attract electrons – the same electrons. Thus, the electrons
are shared tightly between the atoms. The force of attraction that each atom exerts on the shared
electrons is what holds the two atoms together.

The smallest entity of the compounds that are formed is a molecule. The naming of the molecule is by
writing first the name of the lowest electronegative element. Prefixes are used to indicate the number of
each atom present. The second element is changed to end with a suffix -ide as for ionic compounds (for
example CCl4: carbon has the lowest electronegative value so the name is Carbon tetrachloride).

Properties of Covalent (Molecular) Compounds

Covalent Compounds have the following properties:
 Low melting and boiling points
 Do not conduct electricity
 Most are insoluble in water
 Soluble in organic solvents.

Metallic Bond
The metallic bond is formed due to sharing of the valence electrons of the atoms throughout the metal
structure. The model that tends to be applied is Band Theory but for now we can imagine the metal ions
held together by this "sea" of electrons. This allows the metal to be bent and distorted without the
structure breaking. These electrons are also relatively free to move and this explains the high electrical
conductivity of metals.

Properties of Metals
The following are the properties of metals:
 Metals are generally solids at room temperature
 They conduct electricity and heat
 They are malleable
 They have high tensile strength and are usually hard.

Other Types of Bonds

Other bonds, which are equally important, will be mentioned here. Details on how they are formed and
their effect in holding matter together will be encountered as we proceed in the study of this unit.
 Polar bonds
 Dative (covalent) bonding

18
 Hydrogen bonding
 Van der Waals forces
 Dipole interactions

1.7 Chemical Change

A chemical change occurs whenever compounds are formed or decomposed.

Definitions:
 Reactants are substances that are combined to react with each other. They disappear as chemical
change occurs.
 Products are substances produced by the reaction. They appear as chemical change occurs.
 Catalysts are substances which speed up the reaction, but aren't produced or consumed.
The above definitions, in a microscopic sense, can be put as follows: A chemical change occurs whenever
there is a rearrangement of atoms that makes or breaks chemical bonds.

1.7.1 Chemical Reactions

Chemical symbols and formulas are used to describe chemical reactions; they denote substances having
one set of formulas changing into substances having another set of formulas.

Types of Chemical Reactions

Basic types of chemical reactions are mentioned below:
 Synthesis (Combination/Composition): Two or more elements or compounds may combine
to form a more complex compound.
Basic form: A + X → AX.
Example: 2H2 + O2 → 2H2O
 Decomposition: A single compound breaks down into its component parts or simpler
compounds.
Basic form: AX → A + X.
Example: C6H12O6 → 6C + 6H2O
 Replacement: Amore element takes place of another element in a compound and sets the less
active free.

Basic form: A + BX → AX + B or AX + Y → AY + X.
Example of single replacement: Zn + CuCl2 → ZnCl2 + Cu
Example of double replacement: Fe2O3 + 6HCl → 2FeCl2 + 3H2O
 Ionic: These reactions occur between ions in aqueous solutions. A reaction will occur when a
pair of ions comes together to produce at least the following: (i) a precipitate (ii) a gas (iii) water
or some non-ionized substance.

19
 Basic form: AX + BY → AY + BX.

How to Write a Chemical Reaction

As you have seen the above examples of chemical reactions that they can be expressed through equations
that resemble mathematical equations. The reactants appear on the left side of the equation, and the
products are written on the right side of the equation. The reactants and products are connected by an
arrow ( ) some times they will be connected by various types of double arrows. The single arrow shows
that a reaction only proceeds in the direction indicated, while the double arrow indicates that a reaction
can proceed in either direction (that products are also reacting with each other to reform reactants). Thus,
the equation 2Cl Cl2 indicates that two chlorine atoms react to form a molecule of chlorine and that a
reaction can also take place in the reverse direction. This reaction, like all reactions, is affected by
conditions such as temperature. In the case of 2Cl Cl2, the reaction goes to the right at room
temperature (25°C) and to the left only at much higher temperatures (about 500°C). Sometimes the
condition under which a reaction takes place is written over or below the arrow(s) as shown in the general
example below.
Other info
A(aq) B(s) + C(g) + H2O(l) + heat

Where (s) = solid (l) = liquid (g) = gas (aq) = aqueous

 Heat produced: exothermic
 Heat consumed: endothermic
 Other info: heat, pressure, catalysis, etc.

1.7.2 Balancing of Chemical Equations

Given a reaction:

Ca(HCO3)2(aq) CaCO3(s) + CO2(g) + H2O

If you count the atoms of each element involved in the reaction both sides of the equation you will notice
that are all equal. Such an equation is said to be balanced. In order to be consistent with the law of
conservation of mass, all chemical equations must be balanced the law indicates that atoms are neither
created nor destroyed in a chemical reaction.

Activity 5
? Are all chemical equations balanced?

Consider the reaction between sulfuric acid (H2SO4) and sodium hydroxide (NaOH) to form sodium
sulfate (Na2SO4) and water which can be written:

NaOH + H2SO4 H2O + Na2SO4

This is an incomplete equation, since the same number of atoms does not appear on both sides of the
reaction (for example, 1 sodium atom appears in the reactants, but

20
2 sodium atoms appear in the products). Such a reaction could not actually occur. The process of
correcting this fault is called balancing the equation. Placing a 2 in front of the NaOH balances the
number of sodium atoms, as well as the hydrogen and oxygen atoms. The balanced equation is:

2NaOH (aq) + H2SO4 2H2O (l) + Na2SO4 (aq);

This equation implies that two molecules of NaOH are necessary to react with each molecule of H 2SO4.
An equation must be balanced before a chemist can make calculations based on it. Balanced chemical
equations are balanced not only with respect to charge and numbers of each kind of atom but also with
respect to mass. The periodic table lists these atomic weights: H = 1.01, Na = 23.0, O = 16.00, S = 32.1.
So we can identify each atomic symbol with an appropriate mass.

Guidelines to Balancing Chemical Equations

While using the guidelines given below:

Take Note
Remember that in a chemical reaction, matter cannot be created nor destroyed.

 Never touch subscripts when balancing equations since that will change the composition and
therefore the substance itself. The only way to balance an equation is to place numbers, called
coefficients, in front of whole formula/compound. Coefficients apply to the entire molecule that
follows it.

 Check to be sure that you have included all the sources of a particular element that you are
balancing on a particular side since there may be two or more compounds that contain the same
element on a given side.

 You can adjust mono atomic elements towards the end of the balancing act since any change in
their coefficients will not affect the balance of other elements.

 When there are a group of atoms that are acting as a unit such as a poly-atomic ion (e.g. PO43-)
and they appear intact on both sides of the equation, it is best to balance them as a self-contained
group.

 There can't be fractions in the final answer so multiply all the coefficients by LCM of the
denominators of all the fractions appearing in the equation to eliminate the fraction coefficients.

Let us illustrate the use of the guidelines by working through the following example:

Example: Fe2(SO4)3 + K(SCN) → K3Fe(SCN)6 + K2SO4

Solution: The choice of the starting point rests with you. However, it is common practice to begin with
the most complicated compound, in our case K3Fe(SCN)6. By inspection we note that Fe and (SCN) ions
are note shared on same side of the equation. We start to balance these. Since there are two Fe ions on
the left and only one on the right then we place 2 in front of the molecule to become 2K 3Fe(SCN)6. This
changes the quantity of (SCN) ions to become 12. On the left, there is only one (SCN) ion we put 12 as a
coefficient of K(SCN). Our equation becomes:

21
Fe2(SO4)3 + 12K(SCN) → 2K3Fe(SCN)6 + K2SO4

Now we go back to the left and work right. The Fe are balanced the sulfates are not. There are three on
the left, one on the right. We put 3 in front of K2SO4.

Again, let us go left work through right. Fe is OK, SO 4 is OK, K is OK and (SCN) is OK. This is the
final balanced equation:

Fe2(SO4)3 + 12K(SCN) → 2K3Fe(SCN)6 + 3K2SO4

Activity 1.6
? Are all atoms balanced?

22
Lecture 2
The Mole Concept

2.1 Introduction
In this Lecture, we will discuss another important concept that Chemists employ in their
calculations, the mole concept. Before that, we will define and discuss determination of
atomic mass and molar mass. We will further discuss determination of percentage
composition of chemical compounds by mass, combustion analysis and reaction yields.

Learning Objectives
After studying this lecture you should be able to:
 Define atomic mass
 Describe the mole concept
 Define molar mass (molecular weight)
 Determine mass of a given molecule
 Determine percentage composition of elements in a compound
 Define molarity and determine molarity of solutions
 Describe combustion analysis and determine percentage composition of
compounds from their combustion analysis data.
 Describe yield of a chemical reaction and calculate theoretical and
percentage yields of reactions from given information

2.2 Atomic Mass

Atomic mass is defined as the mass of one atom of an element in atomic mass units (amu). The carbon-
12 isotope with exactly 12 amu was chosen as the reference atom. Using the carbon-12 atom as a basis for
all the other elements, proportions were set up and atomic masses were assigned to each of the other
elements.
Atomic masses can be looked up on the periodic table and they are the larger numbers in each box. It is
important to note that the atomic masses are averages of all the isotopes of that particular element. For
example, carbon exists in the form of a carbon-12 atom, carbon-13 atom and carbon-14 atom, and when
the atomic masses were calculated, an average was taken. Below is an example in which the atomic mass
of carbon is solved for.

23
98.89% of all carbon atoms are carbon-12, 1.11% of all carbon atoms are carbon-13. The percentage of
carbon-14 atoms present in all carbon atoms is so small that it plays no part in this calculation.
.9889 (12 amu) + .0111 (13 amu) = 12.01
This is how the atomic mass is calculated.

2.3 The Mole

The mole is the standard method in chemistry for communicating how much of a
substance is present. Even tiny samples of chemicals contain huge numbers of atoms,
ions or molecules. For convenience, chemists have chosen the mole to save as a
reference for a collection of a large number of these species like e.g. a “dozen” is a
reference to a collection of 12 objects. The symbol for mole is mol.

The mole is defined as the amount of matter that contains as many elementary objects as the number of
atoms in exactly 12 grams of carbon-12 (12C).
A number to represent the mole has been very carefully measured in a variety of ways over decades; this
number is 66.0221367 x 1023. This is usually simplified to three (3) figures as 6.02 x 11023, and it is known
as the Avogadro's number, in recognition to Amedeo Avogadro (1776-1881) who was the first person
to realize that equal "amount" of substances contained the same number of atoms. It is abbreviated as
NA.
It is important to remember that when the mole is used, the elementary entities must be specified and may
be atoms, molecules, ions, electrons, other particles, or groups of particles. It is not proper, however, to
use the term mole for a heterogeneous or homogeneous mixture.

? A mole of air is = 6.02 x 1023. Comment on the statement

Worked Examples
1. Calculate the mass in grams of 1.80 x 10 23 molecules of H2O (Given: H = 1.0 g, O = 16.0 g;
Avogadro’s number = 6.02 x 1023)

Soln:
The Avogadro’s number means there are 6.02 x 10 23 molecules per one mole of any substance
Molecular mass of H2O is 18g
Therefore there are 6.02 x 1023 molecules per 18g of H2O
To determine the mass of 1.80 x 1023 molecules f H2O:
6.022 x 1023 molecules ≡ 18 g of H2O
1.80 x 1023 molecules ≡ X g of H2O
X = 1.80 x 1023 molecules x 18g/6.022 x 1023

24
 X = 5.38g of H2O

2.4 Molar Mass (Molecular Weight)

The molar mass is the mass in grams of one mole. One mole
contains 6.022 x 1023 entities.

Therefore, a molar mass is the mass in grams of 6.022 x 10 23 entities. The molar mass of a substance is
the molecular mass in grams. However, remember that compounds, which are ionic, have no “molecular”
weight but formula mass/formula weight in grams.

? How does one calculate a molar mass?

If someone asked right now how much one mole of Helium weighs, the answer would be 4.003 grams,
but if someone asked how much one mole of Al 2S3 (Aluminum Sulfide) weighs, uh??? To do this there is
a basic assumption that has to be put in place. This assumption is that in one mole of Al 2S3, there are two
moles of Al and three moles of S.
So using this assumption, there are 2 moles of Al and 3 moles of S, so take 26.98 grams (which is the
mass of 1 mole of Al) and multiply it by 2 (because there are two moles of Al in Al 2S3). Then take 32.06
grams (which is the mass of 1 mole of S) and multiply it by 3 (because there are three moles of S in Al 2S3).
Then add the two amounts up.
Al+3 = 2 mol Al+3 = 2 (26.98) = 53.96 g
S-2 = 3 mol S-2 = 3 (32.06) = 96.18 g
Total = 150.14 g

Molar mass is the summation of all atomic mass units in the substance

Worked Example
1. Determine the mass of 0.75 mol LiCl.
(Given atomic masses: Li = 7.0 g; Cl = 35.5 g)

Soln:
1 mol of LiCl = (7.0 + 35.5)g
= 42.5g/mol

2. 0.75 mol of LiCl = 0.75 mol x 42.5 g/mol

25
 = 31.875g

EXERCISE 2.1

Determine the mass of each element in the substance.

(1) 0.345 mol LiCl,
(2) 1.98 mol KBr,
(3) 0.57 mol HCl
(4) 0.75 mol of H2SO4

2.5 Percentage Composition by Mass

Percent composition by mass is defined as the percent by mass of an element in a compound. It is

obtained by dividing the mass of an element by the total mass of the compound times 100. So if someone
wanted to find the percent by mass composition of Aluminum and Sulfur in Aluminum Sulfide, he would
proceed as follows:
% Al = (g of Al/g of Al2S3) x 100
% S = (g of S/g of Al2S3) x 100
% Al = (53.96 g / 150.14 g) x 100 = 35.94% Al
% S = (96.18 g / 150.14 g) x 100 = 64.06% S
So, Aluminum sulfide is 35.94% by mass of Aluminum and 64.06% of Sulfur by mass.

EXERCISE 2.2

1. Determine the percent composition of each element in each of

the following compounds.
i. MgS
ii. LiCl
iii. KBr
iv. HCl

2.6 Combustion Analysis

Combustion analysis is a method used in both organic chemistry and analytical chemistry to determine
the elemental composition (empirical formula) of a pure organic compound by combusting the sample
under conditions where the resulting combustion products can be quantitatively analyzed. Once the
number of moles of each combustion product has been determined the empirical formula or a partial
empirical formula of the original compound can be calculated.

26
To perform combustion analysis, an organic compound, usually containing carbon, hydrogen and oxygen
is burnt in a closed container. Chemists must know the mass of the substance before burning it. This is so
that the mass of the products of combustion can be compared to the original total mass. The mass of the
combustion productions can then be used to calculate the number of moles of oxygen, hydrogen and
carbon in the original mass.
Worked Example:
An unknown liquid compound containing carbon, hydrogen and chlorine was found to have a molar
mass of 131.5 g/mol. Upon subjecting it to combustion analysis, a 1.75 g sample of the compound gave
0.121 g of H2O and 1.17 g of CO2. The compound was further subjected to precipitation analysis to
determine the amount of Cl, where 0.655 g of sample gave 2.16 g of AgCl. Determine the molecular
formula of the compound.
(Given: C = 12.0g; H = 1.0g; Cl = 35.5g; Ag = 107.8g)

Solution
Step 1: Use the combustion data to determine the percentage of C and H
CO2 = 12g + 32g = 44g
If 44g of CO2 contains 12g of C, how much C will be contained in 1.17 g of CO 2?
1.17g x 12g/44g = 0.319g of C
Therefore 1.75 of the sample contains 0.319g of C, which is 0.319/1.75 x 100 = 18.2%
H2O = 2g + 16g = 18g
If 18g of H2O contains 2g of H, how much will be contained in 0.121 g of H 2O?
0.121g x 2g/18g = 0.0134g
Therefore 1.75g of the sample contains 0.0134g of H, which is 0.0134/1.75 x 100 = 0.7%
Step 2: Use precipitation data to determine the percentage of Cl
AgCl = 107.8 g + 35.5g = 143.3g
If 143.3g of AgCl contains 35.5g of Cl, how much will be contained in 2.16g?
2.16g x 35.3g/143.3g = 0.535g
Therefore 0.655g of the sample contains 0.535g of Cl, which is 0.535/0.655 x 100 = 81.6%
Now you have the percentage compositions of all three elements in the sample
i.e. C = 18.2% H = 0.7% Cl = 81.6% (you may add them to ensure they are ~ 100)
Step 3: Use this data and the molar mass of the sample compound to determine its formula
C H Cl
18.2/12 = 1.52 0.7/1 = 0.7 81.6/35.5 = 2.3
1.52/0.7 = 2 0.7/0.7 = 1 2.3/0.7 = 3
The compound’s simplest formula is C2HCl3
This is the empirical formula

Step 4: Compare this with its molar mass of 131.5g/mol to get its molecular formula.

27
(2 x 12) + (1 x 1) + (3 x 35.5) = 131.5x
131.5 = 131.5x
x=1
Therefore the molecular formula of the compound is C2HCl3 (trichloroethene)
Menthol, the substance we can smell in mentholated cough drops, is composed of C, H, and O. A 0.1005
g sample of menthol is combusted, producing 0.2829 g of CO 2 and 0.1159 g of H2O. What is the
empirical formula for menthol?

2.7 Reaction Yield

For a given mass of reactants in a chemical reaction it is possible to calculate the maximum possible mass
of a certain product that could be produced.
Balanced chemical equations portray that reactants gives 100% products. This is generally not possible
due to some or all of the following reasons:

 Unfavourable conditions.

 Reaction being stopped before it was complete.

 Side reactions.

 Back reactions leading to equilibrium.

Due to the above reasons reaction yield have to be considered. The yield of a reaction is the amount of
product produced. The theoretical yield is the amount of product that is predicted by the balanced
equation. The actual yield is the amount of product obtained in an experiment. The percent yield
describes what percent of the theoretical yield was actually obtained in an experiment.

Actual yield
%yield   100
Theoretical yield

Given any reactants (e.g. H2 and O2), how much product will be formed?
?

Questions of this type are frequently encountered in the course of studying matter and its
transformations. The mole method becomes very hand in solving such problems. The method is based
on the fact that the stoichiometric coefficients in a balanced equation can be interpreted as the number
of moles of each substance. For example the formation of water:
2H2 + O2 → 2H2O
We read the equation above as 2 moles of hydrogen gas react with 1 mole of oxygen gas to produce 2
moles of water. The following steps should be adhered to when employing the mole method:
i. Make sure the chemical equation is correctly balanced.

28
 ii. Using the molar mass of the substance, convert the mass in the problem to moles.
iii. Construct a molar proportion (two molar ratios set equal to each other). Use it to convert to
moles of the unknown.
iv. Using the molar mass of the unknown substance, convert the moles just calculated to mass

Diagrammatically the steps followed while solving stoichiometric problems can be represented as below:
Mass of Moles of Moles of Mass of
Reactant Reactant Product Product

Let us work out the following problems so as to clarify the application of the mole method concept.
Example:
1. How many grams of AgCl can be formed from 2.00 grams of NaCl and an excess of AgNO3?
Step 1: Write and Balance the equation

AgNO3 + NaCl  AgCl(s) + NaNO3

Step 2: Change mass to moles

number of grams of NaCl 2.00

Number of moles of NaCl  
Molar Mass of NaCl 58.44
Let x = the number of grams of AgCl formed

x
Number of moles of AgCl 
143.32

Step 3: Construct molar proportions.

From the equation we have a 1:1 ratio of NaCl and AgCl
Therefore:
Number of moles of AgCl = Number of moles of NaCl

x 2.00

143.32 58.44
x 
2.00143.32  4.90 grams
58.44
2. A 0.2905 gram sample containing only Pb3O4 and inert matter gives a precipitate of PbSO4
weighing 0.3819 grams. What is the purity of the sample?
From the information given we have:

Pb3O4  3PbSO4

x
No of moles of Pb3O4 =
685.57
29
 0.3819
No of moles PbSO4 =
303.25

x  1   0.3819 
   
685.57  3   303.25 
1  0.3819  685.57
x 
3  303.25
x  0.2878 grams of Pb 3 O 4

No of grams of Pb 3 O 4
% purity =  100 %
No. of grams of sample

0.2878
=  100 %
0.2905
= 99.07 %
These steps are applicable to most of the problems of mass relationships. However, special observation
must be made when dealing with reactions in solution.

2.7.1 Molarity
Instead of using molar mass to convert a mass to moles, you use the volume and molarity of the solution
to get the moles of reactants. The rest of the calculation follows the remaining three steps.

What is molarity?
?
The term concentration is used to indicate the amount of solute dissolved in a quantity of solvent or
solution. The most widely used way of quantifying concentration in chemistry is molarity.

The molarity of a solution is defined as the number of moles of

solute in a litre volume of solution.

moles solute
Molarity 
volume solution litre

How do you calculate the number of moles of solute?

?

conc g/L
(i) moles 
Molecular Mass

30
(ii) conc g/L = moles x Molecular Mass
conc g/L
(iii) Molecular Mass 
moles
The three relationships given indicate that the equation can be employed to solve for any of the items
comprising it depending on the given data.

Dilution

For convenience, solutions are purchased or prepared in concentrated stock solutions, which must be
diluted before use.
When you take a certain volume of stock solution and add solvent to make it into a different volume the
act is known as dilution. During dilution the law of conservation of matter is obeyed since it is only the
molarity, which changes while the number of moles of the molecules in solution is not altered. Therefore:
Moles of solute before dilution = moles of solute after dilution
Or
Number of millimoles of solute before dilution = millimoles of solute after dilution
Or
Number of grams of solute before dilution = number of grams of solute after dilution
Or
Mass % x grams of solution before dilution = mass % x grams of solution after dilution

Dilution is a common task in any laboratory. So it seems logical to have a convenient way
of remembering how to do it.

Starting with the definition of molarity:

moles solute
Molarity  = M = moles of solute/V(s)
volume solution litre
Solving for moles of solute gives:
Moles of solute = M x V (litre)
Or
Millimoles of solute = M x V (mL)
If moles of solute before dilution = moles of solute after dilution then
M x V in litres before dilution = M x V in litres after dilution or
M1V1 = M2V2
Where: M1 = molarity before dilution
V1 = volume of solution before dilution
M2 = molarity of solution after dilution
V2 = volume of solution after dilution
Note: use the formula only for dilution problems, not for problems involving equations. Also make sure
you understand and remember it.

31
Example:
What is the concentration of pure water?
Molecular weight of water = total atomic mass of 2H + O = (2x1.008) + 16.0 = 18.0
Density of H2O = 1 g/mL or 1000 g/L

 1 mole   1000 g 
      55.6 M Pure water is 55.6 M H2O
 18.0 g   L 

32
 Section Summary
This Section consists of two lectures. The first lecture dwelt on defining chemistry and introducing key
concepts which are used in the study of chemistry, including matter and its properties, elements and
compounds. A summary of Daltons Theory which is the basis of the modern chemistry and states that
all matter is composed of tiny, indivisible particles called atoms, that all atoms of the same element are
identical, that compounds contain atoms of different elements combined in whole number ratios, and
that atoms are neither created nor destroyed in chemical reactions (the law of conservation of matter).
This led to discussing about chemical formulas, chemical bonding, writing and balancing chemical
equations. Balanced chemical equations give information which can be utilized in calculations.

The second lecture dwelt on the mole concept. The mole (1 mole = 6.022 × 10 23 particles) is based on
the fact that the stoichiometric coefficients in a balanced equation can be interpreted as the number of
moles of each substance. We further discussed the determination of atomic mass and molar mass,
percent composition of elements in a compound, determination of elemental composition in a
compound by combustion analysis and finally determination of mass yield of products of a chemical
reaction.

Exercise
1. Explain why reactions do not typically give 100% yields.

What is the percent yield for the production of diborane, B2H6? The predicted yield is 126 g and
the actual yield was 81 g? The equation for the reaction is written as: 2 NaBH4(s) + I2(s) →
B2H6(g) + 2 NaI(s) + H2(g)

2. Write balanced equations to represent the following reactions:

(a) The decomposition by heating, of solid ammonium nitrate to produce dinitrogen gas
(laughing gas) and water.

(b) The reaction of aqueous sodium carbonate with hydrochloric acid to produce water,
carbon dioxide gas, and aqueous sodium chloride.

(c) The reaction of methane (CH4) ammonia, and oxygen gases to form gaseous hydrogen
cyanide and water vapour.

3. Which of the following statements are true and which are false?

(a) One mole of KCl is more massive than one more of NaBr.

(b) If F is lighter than Cl, then F- must be heavier than Cl–.

33
 (c) If we are given the molecular mass of NH3, we can deduce the atomic masses of N and
H without further information.

4. The atomic mass of an element X is 33.42 amu. A 27.22 g sample of X combines with 84.10 g of
another element Y to form a compound XY. Calculate the atomic mass of Y in amu.

5. The reaction: Cr2O3 + 3CCl4 → 2CrCl3 + 3CCl2O is used to make CrCl3. In one experiment 6.37
g of Cr2O3 was treated with excess CCl3. Calculate the percent yield of CrCl3.

6. A quantity of 25.0 ml of a 0.866 M HCl solution is poured into a 500 ml volumetric flask and
water is added until the volume of the solution is exactly 500 mL. What is the concentration of
the final solution?

References
1. Tracy Paulsen (2010). Introduction to Chemistry. CK-12 Foundation
2. Petrucci, R. H., Harwood, W. S., Herring, G.E. and Madura, J. (2006) General Chemistry: Principles
and Modern Application, 9th Edition. Prentice Hall.
3. Chang, R. (2003). General Chemistry: The Essential Concepts. 3 rd Ed. The McGrow-Hill
Companies, Inc., New York.
4. Burns, R.A. (2002) Fundamentals of Chemistry 4 th Edition. Prentice Hall.
5. Saylor Foundation (2011) General Chemistry: Principles, Patterns and Applications. eISBN: 978-1-
4533-3122-4.
6. Chang, R. (2003). General Chemistry: The Essential Concepts. 3 rd Ed. The McGrow-Hill
Companies, Inc., New York.
7. Burns, R.A. (2002) Fundamentals of Chemistry 4 th Edition. Prentice Hall.

34
Lecture 3
Atomic Structure

3.1 Introduction
In this Lecture we are going to find out how the substances are formed from fundamental particles and
discuss the description of the atomic structure.

Learning Objectives
After studying this lecture you should be able to:
 Define atom
 Describe the structure of an atom
 Describe relationship of atomic particles
 Describe the arrangement of sub-atomic particles
 Describe the atomic spectra.

3.2 What is an Atom?

All the matter around you is made of atoms, at present there are about 100 kinds of atoms in the entire
universe, and whether these atoms form trees or tyres, ashes or animals, water or the air we breathe,
depends on how they are put together. That is their structures. The same atoms are used again and again.
Chemistry is made intricate and beautiful by the fact that each element reacts in a different way.

? Why is it possible to use atoms again and again?

It is possible to use atoms again and again because matter can be neither destroyed nor created in a
chemical combination. This is in accordance to the Law of Conservation of matter.
The structure determines not only the appearance of materials, but also their properties. It is important to
understand the structure of materials so that you appreciate why an electrical insulator can become a
superconductor, a pencil a diamond, a common cold a deadly virus.

? Are atoms the smallest particles?

The early Scientists believed that atoms were the indivisible, smallest most fundamental unit of matter.
However in the course of research it was discovered that there are smaller particles. The subatomic
particles are electrons, protons and neutrons.

35
3.2.1 Electrons
Through experiments, J. J. Thomson in 1897 discovered one of the fundamental building blocks of
matter, the electron. Electrons are very small (their mass is quite negligible compared with the mass of
the atom) negatively charged particles that are indeed fundamental parts of every atom. Electrons are
parts of all types of matter.

Say whether the statement is true or false:

The electrons emitted by gold are heavier than those emitted by hydrogen gas.
Give an explanation for your choice.

3.2.2 Protons
What was known was, the atom contains electrons which are negatively charged, but the atom was
electrically neutral. This prompted more research. Ten years later, Ernest Rutherford discovered that
atoms have a very dense nucleus, which contains protons.
Protons are charged elementary particles that can exist freely in an atomic nucleus. A proton has a charge
+e, where e is the charge on the electron. Its mass is:
mp = 1.6726 x 10-24g = 1.6726 x 10-27kg = 9.3828 x 102MeV/c2 = 1.0073 amu This mass was
measured experimentally. The ratio of the proton mass to the electron mass is:
mp
 1,836.15
me

Calculate the mass of the electron (me) in g, kg, MeV/c2 and amu

The number of protons in the nucleus of each atom of an element is called the atomic number (Z). In a
neutral atom the number of protons is equal to the number of the electrons, so the atomic number also
indicates the number of electrons present in the atom.

3.2.3 Neutrons
Due to the neutrality of the atoms, it was expected that the ratio of the mass of a helium atom (2 protons)
to that of the hydrogen atom (1 proton) should be 2:1. In reality, however, the ratio is 4:1. Chadwick’s
experiment when he bombarded a thin sheet of beryllium with  particles produced electrically neutral
particles having a mass slightly greater than that of a proton. He called these particles neutrons. The mass
of a neutron is 1.6749 x 10-24g = 1.6749 x 10-27kg.

? What is the importance of the neutrons in the nucleus of an atom?

36
Without neutrons present, the repulsion among the positively charged protons would cause the nucleus to
fly apart. Consider the element helium, which has two protons in its nucleus. If the nucleus did not
contain neutrons as well, it would be unstable because of the electrical repulsion between the protons.
Neutrons add to the strong force of attraction but have no electric charge and so do not increase the
electromagnetic repulsion.

Table 3.1: Mass and charge of subatomic particles

Particle Mass Charge
(g) Atomic mass Coulomb Charge unit
unit (amu)
Electron 9.10939 x 10-28 0.00055 -1.6022 x 10-19 -1
Proton 1.67262 x 10-24 1.0073 +1.6022 x 10-19 +1
Neutron 1.67493 x 10 -24 1.0087 0 0

3.3 Relationship of Atomic Particles

All protons are exactly the same, all neutrons are exactly the same, and all electrons are exactly the same.
Protons and neutrons have almost exactly the same mass. The mass of an electron is almost negligible
compared to the mass of a proton. Electrons have a unit negative charge. Protons each have a positive
charge. The atom's nucleus and electrons are held together by the electromagnetic force; the positive
charges of the protons balance the negative charges of the electrons. Neutrons have no charge.

? What is the identity of the atoms of different elements?

The answer to this question centres on the number of protons in the nucleus of the atom:

All atoms of an element have the same number of protons in the nucleus

The specific number of protons is different for different elements and is called the atomic number. In
other words we are saying that the atomic number is the identity of an element. Furthermore, because an
atom has no net electrical charge, the number of electrons in it must equal its number of protons. For
example, all atoms of the element carbon have six protons and six electrons.

3.3.1 Mass number (A)

We know that except for hydrogen, all atomic nuclei contain both proton and neutrons. The total number
of neutrons and protons present in the nucleus of an atom of an element is the mass number. In general
the mass number is given by:

Mass number = number of protons + number of neutrons

= atomic number + number of neutrons

37
Note that all three quantities; atomic number, mass number and number of neutrons must be positive
integers, or whole numbers.

3.3.2 Isotopes
In most cases atoms of a given element do not have the same mass. Atoms that have the same atomic
number but different mass number are called isotopes. As an example hydrogen has three isotopes; the
normal hydrogen with 1proton, the deuterium with 1proton and 1 neutron and tritium has 1proton and 2
neutrons.
The accepted way to denote the atomic number and mass number of an atom of element Y is as follows:
mass number
A
zY

atomic number
Thus, for the isotopes of hydrogen, we denote:
1 2 3
1 H 1 H 1 H
hydrogen deuterium tritium
Another example is of the isotopes of uranium with mass numbers of 235 and 238 respectively:
235 238
92 U 92 U

Chemical symbols of elements are represented with mass number as

superscript and the atomic number as subscript.

Because all atoms of a given element have the same atomic number, the subscript is redundant and hence
is often omitted. The isotopes are represented by their mass number. For example, some carbon atoms
contain six protons and eight neutrons and are consequently represented as 14C (read "carbon fourteen").

? Is it safe now, to say atoms are the smallest particles of an element?

The difference between atoms of distinct elements (gold and hydrogen, for example) is due entirely to the
difference in the number of subatomic particles in each atom. This is because all atoms are made up of
protons, neutrons, and electrons and these particles are the same in all atoms. We can therefore consider
an atom to be the smallest particle of an element because breaking an atom into subatomic particles
destroys its identity.

Worked Examples 3.1

In order to work out these examples you need information which can be obtained from the periodic table
in appendix A.
(1) How many protons, neutrons, and electrons are in an atom of 197Au?
Answer: The superscript 197 is the mass number, the sum of the numbers of protons and
neutrons. According to the list of elements given on the front inside cover of this text, gold has

38
 an atomic number of 79. Consequently, an 197Au atom has 79 protons, 79 electrons, and 197 - 79
= 118 neutrons.
(2) How many protons, neutrons, and electrons are in a 39K atom?
Answer: 19 protons, 19 electrons, and 20 neutrons.
(3) Two isotopes of mercury, with mass numbers 199, and 200. Write the complete chemical symbol
for each of them.
Answer: Mercury has atomic number 80, so all atoms of mercury contain 80 protons. The two
199 200
isotopes are therefore represented by 80 Hg and 80 Hg

Give the complete chemical symbol for the nuclide (an atom) that contains 18 protons,
? 18 electrons, and 22 neutrons.

3.4 Discovery and Arrangement of Subatomic Particles in the

Atom

The idea was started by Ernest Rutherford; however, it was his colleagues experiment conducted in 1909
which demonstrated that atoms have most of their mass and positive charge concentrated in a nucleus. In
the gold foil experiment, alpha particles (emitted by polonium) were shot through a sheet of gold.
Rutherford observed that most of the particles passed straight through the sheet with little deflection
(striking a fluorescent screen on the other side). About 1 in 8000 of the alpha particles, however, were
heavily deflected (by more than 90 degrees). This led to the planetary model of the atom in which point-
like electrons orbited in the space around a massive compact nucleus like planets orbiting the Sun.
Scattered beam
(small deflection) movable
Scattered beam flourescent
(large deflection) screen

Transmitted
beams with
little or no
deflection
gold foil

Beam of
alpha
particles Lead screen
Radioactive with slit
source
Figure 3.1: The Rutherford gold-foil experiment
The neutrons and protons are in the centre of the atom in a nucleus. The electrons are outside the
nucleus in electron shells that are in different shapes at different distances from the nucleus. The atom is
mostly empty space. Almost all the mass of an atom is concentrated in the tiny nucleus. The electrons are
constantly spinning around the nucleus of the atom.

39
Figure 3.2: The Rutherford atomic model, as shown for a neon atom

3.4 1: Behaviour of the Electrons in the Atom

The Rutherford atomic model could not answer all the questions of the scientists of that time. This
prompted Niels Bohr to suggest another model. Bohr developed a mathematical model for the behaviour
of an electron in the hydrogen atom based on the Rutherford atom and quantum theory of Planck.

3.4.2 Quantum Theory

(i) Atoms can exist in certain states characterized by definite amounts of energy. When an atom changes
its state, it absorbs or emits an amount of energy (electromagnetic radiation) just sufficient to bring it
to another state.
(ii) When atoms absorb or emit light in moving from one energy level to another, the wavelength of the
light is related to the energies of the two states by the equation:
Efinal – Einitial = hc/
Where h = Planck’s constants = 6.626 x 10-34 J.s/particle
c = speed of light = 2.998 x 108 m/s

(iii) The allowed energy states of atoms can be described by sets of numbers called quantum numbers.
Quantum numbers are associated with individual electrons in an atom.

Before we discuss the Bohr hydrogen atom and quantum numbers let us revisit the electromagnetic
spectrum.

3.4.3 Atomic Spectra

The spectrum of white light is a continuous band which contains wavelengths of varying lengths. White
light is one form of electromagnetic radiation (radio waves, x-rays and gamma-rays are other examples).

40
All forms of electromagnetic radiation exhibit wavelike behaviour. They all can be characterised by a
wavelength,  and frequency, . The wavelength and frequency are related to speed of light, c as follows:
 = c
Electromagnetic radiation also has properties associated with particles called photons. The light emitted
when an electron moves from an orbit with higher n value to one with a smaller n value is a photon. The
energy of a photon may be determined from the expression:
hc
E  hv 

When one heats up a gas, it emits light of various wavelengths. When this light is passed through a prism
it consists of only a limited number of coloured lines with dark spaces between them. Each of these lines
corresponds to a single wavelength of light, so the light emitted by such a gas consists of light of discrete
energies. These discontinuous spectra are called atomic spectra.
Each element has its own distinctive line spectrum, a kind of atomic fingerprint. For monoatomic gases
formed of only one kind of atom the emission spectra contains only light of particular wavelength.
For example:
Element Colour (wavelength)
cesium Sky blue
rubidium Deepest red
hydrogen Reddish purple

For hydrogen the spectra obeys the relation:

1  1 1 
 R H  2  2 
λ  nf ni 

Where ni and nf are positive non-zero integers with ni > nf and RH is a constant called Rydberg’s
constant with the value RH = 1.097 x 107 m-1.
One of the first such series of lines discovered which obey the equation was found by Balmer, which
corresponds to nf = 2 and is in the visible light. The fact that atomic spectra consists of only limited
numbers of well-defined wavelength lines provides a great opportunity to learn about the structure of
atoms. For example it suggests that only a limited number of energy values are available to excited
gaseous atoms.

3.4.4 The Bohr Theory of the Hydrogen Atom

The hydrogen atom has a central proton and a single electron which moves around the proton in a
circular orbit. The force of attraction of the proton for the electron is related to the circular motion of the
electron. The energy of the electron was expressed in terms of the radius of the orbit.

The Bohr Theory predicts the radii of the allowed orbits in a hydrogen atom
Rn = n2ao
Where ao = 0.53 Å (53 nm)

41
 ? Is it possible to know the energy of the electron?

Also, Bohr found the allowed energies are restricted. The energy of an energy level is given by the
equation:
E = -B/n2
Where n = 1, 2, 3, …
B = 2.179 x 10-18 J/particle
E = -2.179 x 10-18 J/particle/n2 = -1312 kJ/mol/n2

3.4.5 Quantum Numbers

Quantum numbers are the “addresses” for electrons. The address of a place has several points (street,
postal number, etc) which specify the place. Likewise the electron can be identified by four quantum
numbers which are explained below:
(i) The principal quantum number, n

This number determines the size of an orbital (bigger n = bigger orbitals). It largely determines the energy
of the orbital (bigger n = higher energy). The n can take on integer values n = 1, 2, 3, ...,∞. All electrons in
an atom with the same value of n are said to belong to the same shell. The shells have been assigned
names by spectroscopists as follows:

Table 3.2: Spectroscopist’s notation for shells

n Shell name n Shell name
1 K 5 O
2 L 6 P
3 M 7 Q
4 N

(ii) The Azimuthal Quantum Number, 

This number  designates the overall shape of the orbital within a shell, it affects orbital energies (bigger
 = higher energy). All electrons in an atom with the same value of  are said to belong to the same
subshell. The number  can take only integer values between 0 and n-1. In some books it is referred to
as the orbital angular momentum quantum number. Spectroscopists use the following notation for
subshells

Table 5: Spectroscopist’s notation for subshells

 Subshell name
0 s
1 p
2 d
3 f

42
(iii) The Magnetic Quantum Number, mℓ

This number determines the orientation of orbitals within a subshell. It does not affect orbital energy
(except in magnetic fields!). The m  can only take integer values between -ℓ and +ℓ with 0 inclusive. The
number mℓ is related to orbitals as follows; the number of mℓ values within a subshell is the number of
orbitals within a subshell.

Table 3.3: Number of orbitals in subshells

ℓ Possible values of mℓ Number of orbital in
this subshell
0 0 1
1 -1, 0, +1 3
2 -2, -1, 0, +1, +2 5
3 -3, -2, -1, 0, +1, +2, +3 7

Note: Orbitals in a subshell have the same energy (degenerate) e.g. the 3-p orbitals are of the same
energy; the 5-d orbitals all are of the same energy and so forth. However, the degeneracy is lost when
magnetic field is applied.

(iv) The Spin Quantum Number, ms

This number helps to explain several experimental observations when the electron is treated as though it
were spinning. The spin makes the electron behave like a tiny magnet. Spin can be clockwise or counter
clockwise. Spin quantum number can have values of +½ or -½. These are denoted as  for +½ or  for -
½ spins.

43
Lecture 4
The Periodic Table of Elements

4.1 Introduction

This Lecture describes the Periodic Table of elements and the distinction between different types of
elements such metals, nonmetals, and metalloids. It also explains the arrangement of electrons in shells,
sub-shells and orbitals of the atom, quantum numbers and the periodic variations in physical properties.

Learning Objectives

After studying this lecture you should be able to:

 Define the periodic table of elements
 Describe trends and properties of groups of elements in the periodic table
 Write electron configuration of atoms and ions
 Describe quantum numbers
 Describe variations in physical properties of elements in the periodic table

4.2 The Periodic Table of Elements

The Periodic Table is a tabular arrangement of the chemical elements, ordered by their atomic number
(number of protons), electron configurations, and recurring chemical properties. Elements in the Periodic
Table are arranged in such a way that those with similar chemical properties are on the same column.
All the elements are listed in a table, which have certain characteristics to facilitate the identification. It
shows the element’s weight and the number of protons of each element in an organized manner also it is
used to show trends, similarities, and differences of elements. The periodic table is exactly what its name
is, a table, so it has columns and rows. The rows are called periods. The columns are called families or
groups. Each group (column) of elements has similar chemical properties (see appendix 1).
There are three classifications for the elements. There are metals, nonmetals and metalloids. The pure
elements are rarely found in nature. The elements are typically combined with one another to form
compounds. Gold and platinum are two that are found pure in nature.
Metals are usually solids at room temperature, good conductors of heat and electricity, are ductile and
malleable. They make up the largest part of the periodic table. The nonmetals have the opposite
properties of metals. There are seventeen (17) nonmetals. Eleven of these are gases, one is a liquid and
five are solids at room temperature. Nonmetals are poor conductors of heat and electricity; they are
neither malleable nor ductile. The seven (7) metalloids are the smallest class of elements. They have some
properties like metals and some properties like nonmetals. Silicon, Si, in Group 4a is one of the most well
known semimetals or metalloids. Metals like iron usually have high melting points. However, mercury,

44
Hg, has a low melting point. Metals can be hammered into thin sheets this makes them malleable. Gold is
one of the most malleable metals. Gold foil is used for decoration.
For convenience, some element groups have special names. The group 1A elements (Li, Na, K, Rb, Cs,
and Fr) are called alkali metals, and the group 2A elements (Be, Mg, Ca, Sr, Ba, and Ra) are called
alkaline earth metals. Elements in group 7A (F, Cl, Br, I, and At) are known as halogens and those in
group 8A (He, Ne, Ar, Kr, Xe, and Rn) are called noble gases or rare gases.

EXERCISE 4.1
Write the names and symbols for four elements in each of the following categories.
(a) Nonmetals
(b) Metals
(c) Metalloids
(d) Give two differences between a metal and a nonmetal.

4.3 Electron Configuration of Atoms (ee)

? How are the electrons arranged in shells, subshells and orbitals of the atoms?

The electron configuration of an atom is the designation of how electrons are distributed among various
orbitals in principal shells and subshells. There are guidelines to follow when assigning electrons to
orbitals.

4.3.1 Guidelines for Predicting the Electron Configuration of an Atom in its

Ground State
1. The Aufbau principle: Electrons occupy orbitals in a way that minimizes the energy of the atom. In
other words, we say, the arrangement of the electrons in an atom is usually that of the lowest energy,
an arrangement known as the ground state. Now, the lower energy states of atoms are those in which
the negatively charged electrons spend more time closer to the positively charged nucleus, and in
general, the lower the principal quantum number of a shell, the closer to the nucleus are its electrons
likely to be found. The first electron that is placed in a set of atomic orbitals goes into the 1s orbital.
When the 1s orbital is filled, the next electron goes into the 2s orbital, and so on. The order of filling
orbitals has been established by experiments, with the exception of a few elements, the order in
which orbitals fill is: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p. Figures 4.1
can help you remember the order of orbital energies.

45
 1s

2s 2p

3s 3p 3d

4s 4p 4d 4f

5s 5p 5d 5f

6s 6p 6d 6f

7s 7p

Figure 4.1: The order in which atomic sub-shells are filled in a many-electron atom.

The Pauli Exclusion Principle states that no two electrons in an atom may have all four quantum numbers
alike. This can be stated in a different way that only two electrons may occupy the same orbital and these
electrons must have opposing spins. This means that 1s orbital is filled when it contains two electrons:
one with n = 1, l = 0, m = 0 and s = +½; the other with n = 1, l = 0, m = 0 and s = -½. These are the
only combinations for a 1s orbital; a third electron must occupy the 2s orbital. The 2s sub-shell consists
of one orbit, because of the limit of two electrons per orbital, thus it can accommodate two electrons, and
the 5th electron would have to occupy the 2p sub-shell.

? How many electrons fill the p sub-shell?

The p sub-shell has 3 orbits. Each orbit has room for 2 electrons. Therefore the total number of electrons
is equal to 2 x 3 = 6 electrons. Generally, to get the number of electrons for each sub-shell you double the
number of orbitals.

? What happens to the 11th electron?

Using figure 4.3, the next sub-shell after 2p is 3s. The 11th electron would occupy sub-shell 3s and so on.

When orbitals of identical energy are available e.g. 2p, the filling of these orbitals follow Hund’s rule:

Hund’s rule: states that an atom tends to have as many unpaired

electrons as possible.

46
Therefore the electrons will occupy the orbitals singly with the same spin.

3p3

Remember that the direction of electron spin has no effect on the energy of the electron.
Electrons that have opposite spins are said to be paired that is ms = +½ for one electron and ms = -½ for
the other.

Alternately, we can state Hund’s rule as follows: the most stable arrangement of electrons in sub-
shells is the one with the greatest number of parallel spins.

The three guidelines discussed above, help us predict the electron configurations of the atoms in their
ground states.
In a shell atoms are filled starting with the lowest orbital. A list showing how many electrons are in each
orbital or subshell in an atom or ion is the electron configuration. The electrons are listed in subshell
notation. Subshell notation: list subshells of increasing energy, with number of electrons in each subshell
as a superscript.

Examples 4.1
1s2 2s2 2p5 means "2 electrons in the 1s subshell, 2 electrons in the 2s subshell, and 5 electrons in the 2p
subshell".

1s2 2s2 2p6 3s2 3p3 is an electron configuration with 15 electrons total; 2 electrons have n=1 (in the 1s
subshell); 8 electrons have n=2 (2 in the 2s subshell, and 6 in the 2p subshell); and 5 electrons have n=3
(2 in the 3s subshell, and 3 in the 3p subshell).

Let us fill the electron configuration for the first 11 element in their ground state. Ground state is the
lowest energy state for an atom or molecule. When an atom is in its ground state, its electrons fill the
lowest energy orbitals completely before they begin to occupy higher energy orbitals, and they fill
subshells in accordance with Hund's rule.

Table 4.1: Electron configurations of the first 11 elements, in subshell notation

Atoms Atomic number (Z) Groundstate electronic configuration
H 1 1s1
He 2 1s2
Li 3 1s2 2s1
Be 4 1s2 2s2
B 5 1s2 2s2 2p1
C 6 1s2 2s2 2p2
N 7 1s2 2s2 2p3
O 8 1s2 2s2 2p4
F 9 1s2 2s2 2p5
Ne 10 1s2 2s2 2p6
Na 11 1s2 2s2 2p6 3s1

47
Notice how configurations can be built by adding one electron at a time.

4.3.2 Writing Electron Configurations

The method employed in writing electron configurations is known as Aufbau principle. This principle is
an approximate procedure for writing the ground state electronic configuration of atoms. The
configuration of an atom is obtained by inserting one electron into the configuration of the atom
immediately to its left on the periodic table. The electron is inserted into the subshell indicated by the
element's period and block. That is start with hydrogen, and builds the configuration one electron at a
time.
1. Fill subshells in order by counting across periods, from hydrogen up to the element of interest as
the arrows indicate in Figure 4.1.
2. Rearrange subshells (if necessary) in order of increasing n and ℓ

Examples: Give the ground state electronic configurations for: Al, Fe, Ba and Hg
Al: 1s2 2s2 2p6 3s2 3p1
Fe: 1s2 2s2 2p6 3s2 3p6 4s2 3d6
Ba: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2
Hg: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10

The Aufbau principle does not hold with d and f block elements; orbital interactions cause exceptions
such that half-filled and completely filled d and f subshells have extra stability.

Table 4.2: Exceptions to the Aufbau principle in the 4 th period

Exception Configuration predicted by True ground state configuration
Aufbau principle
Cr 1s2 2s2 2p6 3s2 3p6 3d4 4s2 1s2 2s2 2p6 3s2 3p6 3d5 4s1
Cu 1s2 2s2 2p6 3s2 3p6 3d9 4s2 1s2 2s2 2p6 3s2 3p6 3d10 4s1

4.3.3 Electron Configurations Including Spin

Unpaired electrons give atoms (and molecules) special magnetic and chemical properties. When spin is of
interest, count unpaired electrons using orbital box diagrams. Examples of ground state electron
configurations in the orbital box notation that shows electron spins are indicated below:

Steps in drawing the orbital box diagrams

First we write the electron configuration in subshell notation
Then we draw a box for each orbital.

Remember that s, p, d, and f subshells contain 1, 3, 5, and 7 degenerate orbitals, respectively. A set of
orbitals are said to be degenerate if they all have the same energy. This degeneracy can sometimes be
"lifted" by external electric or magnetic fields. Remember also that an orbital can hold 0, 1, or 2 electrons
only, and if there are two electrons in the orbital, they must have opposite (paired) spins (refers to Pauli’s
Exclusion Principle).

Pauli’s Exclusion Principle states that a maximum of two electrons can occupy
an atomic orbital – and these electrons must be opposite spin.

48
In other words, we are saying that no two electrons in an atom can have the same set of 4 quantum
numbers. Because the n, ℓ and mℓ quantum numbers address a particular orbital, and the ms quantum
number has only two possible values.

1. Within a subshell (depicted as a group of boxes), spread the electrons out and line up their spins as
much as possible (according to Hund's rule).

Hund's rule states that every orbital in a subshell is singly occupied with one
electron before any one orbital is doubly occupied, and all electrons in singly
occupied orbitals have the same spin.

The number of unpaired electrons can be counted experimentally. Configurations with unpaired electrons
are attracted to magnetic fields (paramagnetism). Paramagnetic materials are attracted to a magnetic field
due to the presence of at least one unpaired spin in their atoms or molecules. Configurations with only
paired electrons are weakly repelled by magnetic fields (diamagnetism). Diamagnetic materials are very
weakly repelled by magnetic fields. The atoms or molecules of diamagnetic materials contain no unpaired
spins.

4.3.4 Core and Valence Electrons

Chemistry involves mostly the shell with the highest value of principal quantum number, n, called the
valence shell.

What is a valence shell?

?

The valence shell is the outer most shell in an atom. If the valence shell is removed what remains is called
a core. The core resembles the inert gases configurations and is chemically inert. We simplify the notation
for electron configurations by replacing the core with a noble gas symbol in square brackets:

Table4.3: Examples of electron configurations written with the core/valence notation

Atom Full configuration core Valence Full configuration
configuration using core/valence
notation
O 1s2 2s2 2p4 He 2s2 2p4 [He] 2s2 2p4
Cl 1s2 2s2 2p6 3s2 3p5 Ne 3s2 3p5 [Ne] 3s23p5
Al 1s2 2s2 2p6 3s2 3p1 Ne 3s23p1 [Ne] 3s2 3p1
Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6 Ar 3d6 4s2 [Ar] 3d6 4s2
Ba See (writing electron conf.) Xe 6s2 [Xe] 6s2
Hg See (writing electron conf.) Xe 6s2 4f14 5d10 [Xe] 4f14 5d10 6s2

Electrons in d and f subshells outside the noble gas core are called pseudocore electrons.

49
Table 4.4: Examples of electron configurations containing pseudocore electrons:
Atom core pseudocore valence Full configuration
Fe Ar 3d6 4s2 [Ar] 3d6 4s2
Sn Kr 4d10 5s2 5p2 [Kr] 4d10 5s25p2
Hg Xe 4f14 5d10 6s2 [Xe] 4f14 5d10 6s2
Pu Rn 5f6 7s2 [Rn] 5f6 7s2

4.4 Quantum Numbers and the Periodic Table

In the following sections we will use the periodic table to explore the connections between the properties
of the elements and their electron configurations. An element's location on the periodic table reflects the
quantum numbers of the last orbital filled.
The period (row) indicates the value of principal quantum number for the valence shell (n = 1, 2, 3…).
The lanthanides and actinides are in periods 6 and 7, respectively. The block indicates value of azimuthal
or orbital angular momentum quantum number ( ) for the last subshell that received electrons in building
up the electron configuration. Blocks are named for subshells (s, p, d, f). Each block contains a number of
columns equal to the number of electrons that can occupy that subshell The s-block (the first 2 columns
on the left of the periodic table) has 2 columns, because a maximum of 2 electrons can occupy the single
orbital in an s-subshell. The p-block (six columns on the extreme right of the periodic table) has 6
columns, because a maximum of 6 electrons can occupy the three orbitals in a p-subshell. The d-block
(columns between s and p subshells) has 10 columns, because a maximum of 10 electrons can occupy the
five orbitals in a d-subshell. The f-block (two rows below the d-block) has 14 columns, because a
maximum of 14 electrons can occupy the seven orbitals in a f-subshell.

4.4.1 Factors Affecting the Valence Shell

Anything that influences the valence electrons will affect the chemistry of the element. There are several
factors which influence the valence shell. Three of the most important factors are listed in order of
decreasing importance.

Factor Effect
1. valence principal quantum Larger n means a larger valence shell (because n controls the
number n size of orbitals)
2. nuclear charge Z Larger Z means a smaller valence shell (because higher
positive charge on the nucleus attracts the valence electrons,
and pulls them inward)
3. number of core electrons More core electrons means a larger valence shell (because
highly penetrating core electrons repel valence electrons, and
push them farther from the nucleus)

50
4.5 Periodic Variation in Physical Properties

4.5.1 Atomic Radius

? What does atomic radius really mean?

We know that an orbital has no definite size. It is simply a probability map describing the probable
location of an electron. We know that an atom consists of a nucleus and electrons that exit in orbitals,
outside the nucleus forming an electron cloud. The size of an orbital is not precisely defined, so the size
of an atom cannot be precisely defined. However, it is possible to estimate the size of an atom. By
studying solid crystalline structures of elements and compounds through a technique known as X-ray
diffraction, an estimate of the distance between the different nuclei of the crystal can be obtained.
Scientists have also been able to estimate the distance between the nuclei of diatomic molecules. By
knowing the distance between nuclei of atoms, scientists may estimate the size of the atom. Atomic
Radius is half the distance between the nuclei of atoms.
We know that atoms have no definite surface. However, a simple model is presented as bound atoms are
like touching spheres. When we add atomic radii for two bound atoms we get an estimate of bond length.

The atomic radius is one-half the distance For diatomic elements ,the radius of the atom is
between the centres of two adjacent atoms. one-half the distance between the centres of the
atoms of the molecule.
Figure 4.3: Atomic radii (metallic radii for metals and covalent radii for nonmetals)

Atomic Radius Periodic Trends

1. As you go right across main group rows, there is no change in valence n, but the charge Z
increases and the number of core electrons remain the same. The net effect on atomic radius as a
result of the increased Z causes a decrease in radius.
2. Going right across transition series, there is no change in valence n, but there is an increase in
both the Z and core electrons. The increase in Z causes a decrease in radius, but the increase in
the number of core electrons causes an increase. The two competing effects cause a small
decrease, then small increase!
3. Going down groups, there is an increase in three factors namely valence n, charge Z and core
electrons. Among the three competing effects, n is the strongest, so radius increases.

51
4.5.2 Ionic Radius
Ionic radius is the radius of a cation or an anion. The periodic trends of ionic radius parallel those of
atomic radius. Cations are always smaller than the parent atom because removing electron decreases
electron-electron repulsion, so the electron clouds contract. Emptying the valence shell completely
(remove all valence electrons) leaves only electrons with lower n value. Anions are always larger than the
parent atom because adding an electron to an atom increases electron-electron repulsion and swells the
electron cloud.

4.5.3 Isoelectronic Ions

Isoelectronic ions are ions that have the same number of electrons. When you compare radii for
isoelectronic ions and atoms you find that size within isoelectronic series is affected only by Z.

Example 4.2
(a) F-, Ne, and Na+ are isoelectronic, with Z = 9, 10, and 11, respectively. All have identical valence n and
identical numbers of electrons, so the larger Z is, the smaller the atom or ion. Na + is the smallest and F- is
the largest.
(b) S2-, Cl-, K+, Ca2+; the number of electrons is 18 for the ions. S2- has 16 protons, a nuclear charge of
+16; Cl- has 17 protons, a nuclear charge of +17; K+ has 19 protons, a nuclear charge of +19; Ca +2 has 20
protons, a nuclear charge of +20.
We expect the Ca+2, with the greatest nuclear charge will have a greatest attraction of its electrons. S 2- has
the smallest nuclear charge will not have as much pull of its electrons toward the nucleus. Therefore, the
ionic size trend will be:
Ca+2 < K+ < Cl- < S2-
(smallest) (largest)

For isoelectronic ions, the radius decreases as the positive nuclear charge
increases.

Ionization Energy
Ionization energy is the minimum amount of energy required to remove an
electron from an atom or ion in gas phase

Normally, ionization removes valence electrons first. This is because valence electrons are farthest from
nucleus on average, so they feel the least attraction for the nucleus and are easiest to remove. End of
valence electrons is marked by a big jump in ionization energies as shown by ionization of the first two
electrons of sodium. Remember that sodium has only one electron in its valence shell.
Na(g)  Na+(g) + e- H = +496 kJ First ionization energy
Na+(g)  Na2+(g) + e- H = 4560 kJ Second ionization energy

? Why such a big jump?

52
Core orbitals have lower n, and are much more penetrating than valence orbitals. Proximity to nucleus
makes core electrons much more difficult to remove. Core noble gas configurations have high stability

Factors affecting ionization energy

(a) Atomic radius: smaller atoms hang on to valence electrons more tightly, and so have higher
ionization energy.
(b) Charge: the higher the positive charge becomes, the harder it is to pull away additional electrons.
The second ionization energy is always higher than the first.
(c) Orbital penetration: It's easier to remove electrons from p orbitals than from s orbitals.
(d) Electron pairing: within a subshell, paired electrons are easier to remove than unpaired ones.
Why? This is because repulsion between electrons in the same orbital is higher than repulsion
between electrons in different orbitals.

Example 4.3
On the basis of gross periodic trends, one might expect O to have higher ionization energy than N.
However, the ionization energy of N is 1402 kJ/mol and the ionization energy of O is only 1314 kJ/mol.
Why? Taking away an electron from O is much easier, because the O contains a paired electron in its
valence shell which is repelled by its partner.

53
 Section Summary
Cathode-ray research led to the discovery of the electron – a fundamental particle of all matter and the
basic unit of negative electric charge. A more complete description of the atomic nucleus was made
possible by the latter discovery of the proton and neutron.

The periodic table is a listing of the elements organized into horizontal rows (periods) and vertical
columns (groups) and according to atomic number. Each group in the table consists of elements with
similar physical and chemical properties.

The properties of an element are related to the electron configuration of its atoms, and elements in the
same group of the periodic table have similar electron configurations.

The metallic and non metallic characters of atoms can be related to a set of atomic properties. In
general, large atomic radii and low ionization energies are associated with metals; small atomic radii, high
ionization energies are associated with non-metals. The magnetic properties of an atom or ion stem
from the presence or absence of unpaired electrons

Exercise

1. Arrange the following species in order of increasing

112 40 122 59 120 58 39
50 Sn 18 Ar 52 Te 29 Cu 48 Cd 27 Co 19 K
(a) number of electrons
(b) number of neutrons
(c) mass
2. Write an appropriate symbol for species containing of 29 protons, 34
neutrons and 27 electrons
3. Give the number of protons, neutrons, and electrons in each of these
species:
a  17
8 O b 199
80 Hg and c 200
80 Hg
4. Write the electronic configuration of the following by using the core/valence
notation:

54
 (a) O (b) Na (c) Ne (d) Ca (e) K

5. Write the electronic configuration of the following:

(a) Na+ (b) Ca2+ (c) Cl- (d) F-

6. Explain the Periodic Table of Elements

7. Refer to the periodic Table of Element and mention the following;
(a) The element that is in group 4A and the fourth period
(b) Two elements with properties similar to those of molybdenum (Mo)
(c) The ion most likely formed from a strontium atom

References
1. Tracy Paulsen (2010). Introduction to Chemistry. CK-12 Foundation
2. Petrucci, R. H., Harwood, W. S., Herring, G.E. and Madura, J. (2006) General Chemistry:
Principles and Modern Application, 9th Edition. Prentice Hall.
3. Chang, R. (2003). General Chemistry: The Essential Concepts. 3 rd Ed. The McGrow-Hill
Companies, Inc., New York.
4. Burns, R.A. (2002) Fundamentals of Chemistry 4th Edition. Prentice Hall.
5. Saylor Foundation (2011) General Chemistry: Principles, Patterns and Applications. eISBN: 978-
1-4533-3122-4.
6. Chang, R. (2003). General Chemistry: The Essential Concepts. 3 rd Ed. The McGrow-Hill
Companies, Inc., New York.
7. Burns, R.A. (2002) Fundamentals of Chemistry 4 th Edition. Prentice Hall.

55
Lecture 5
Properties of Gases

5.1 Introduction
In Lecture One, Section 1.3.1 we explained that gas is one of the main states of matter (solids, liquids,
gases, plasmas). In this lecture we describe gases in terms of their properties: pressure, volume,
temperature, and amount of substance. We will show how experimental relationships (laws) connect the
properties of gases and we will examine a detailed but idealized molecular model of gases and show how
real gases depart from this ideal.

Learning Objectives
After studying this lecture you should be able to:
 Explain what gas is
 Describe properties of a gas
 Explain what pressure is
 Explain how to predict and measure pressure experimentally.
 Describe experiments that show relationships between pressure, temperature,
volume, and moles for a gas sample

5.2 Definition of Gas

Gases are not familiar in everyday life. Unlike solids, gases have no definite shape. Unlike liquids, gases
have no definite volume, but they completely fill a container. The volume of the container is the volume
of the gas in it. A gas exerts a pressure on all sides of the container that holds it. Gas can be compressed
by pressures greater than the pressure the gas on its container. The words vapour, fumes, air, describes a
gas. Air describes the common mixture of gases in the atmosphere. In short we can define gas as follows:

A gas is a phase of matter with neither fixed shape nor fixed volume

Table 5.1 gives elements and compounds which are gases under normal atmospheric conditions, which
are defined as 25 oC and 1 atmosphere (atm) pressure.

56
Table 5.1: Some substances found as gases at 1 atm and 25 oC
Elements Compounds
H2 (molecular hydrogen) HF (hydrogen fluoride)
N2 (molecular nitrogen) HCl (hydrogen chloride
O2 (molecular oxygen) HBr (hydrogen bromide)
O3 (ozone) HI (hydrogen iodide)
F2 (molecular fluorine) CO (carbon monoxide)
Cl2 (molecular chlorine) CO2 (carbon dioxide)
He (helium) NH3 (ammonia)
Ne (neon) NO (nitric oxide)
Ar (argon) NO2 (nitrogen dioxide)
Kr (krypton) N2O (nitrous oxide)
Xe (xenon) SO2 (sulfur dioxide)
Rn (radon) H2S (hydrogen sulfide)

It is easier to describe a gas in terms of its properties: pressure, volume, temperature and amount of
substance.

5.3 Properties of Gases

Gases have three characteristic properties:
(1) They are easy to compress
(2) They expand to fill their containers
(3) They occupy far more space than the liquids or solids from which they form.

Because most gases are difficult to observe directly, they are often described through the use of four
physical properties or characteristics:
 Pressure
 Volume
 Temperature
 Number of particles (moles)

5.3.1 Pressure
Let us describe what pressure is. Pressure is a measure of the force applied (i.e. by a gas or an object due to
its weight) per unit area of a material against which the force is applied.

Pressure = force/area
You will encounter the following units when dealing with pressure.
Table 5.2: Units of pressure

57
 units symbol conversions
pascal Pa 1 Pa = 1 N/m2
psi lb/in2
atmosphere atm 1 atm = 101325 Pa = 14.7 lb/in2
bar bar 1 bar = 100000 Pa
torr torr 760 torr = 1 atm
Millimeters of mercury mmHg 1 mmHg = 1 torr

5.3.2 Atmospheric Pressure

The force experienced by any area exposed to Earth’s atmosphere is equal to the weight of the column of
air above it.

Atmospheric pressure is the pressure exerted by Earth’s atmosphere

The actual value of the atmospheric pressure depends on location, temperature, and weather conditions.

? How is atmospheric pressure measured?

In Figure 5.1 the mercury falls until the pressure due to the weight of the mercury column (acting at the
level of the surface of the mercury in the reservoir) is just equal to the pressure exerted by the
atmosphere. In other words, the height, H, gives us a measure of the strength of the atmospheric
pressure. If the pressure of the air increases a little more mercury will be pushed into the tube and H will
increase.

Normal (or standard) atmospheric pressure is strong enough to support a column of mercury 760 mm
high. This explains why pressures are often stated in mmHg. We say that normal atmospheric pressure is
equivalent to 760 mmHg. Alternatively, a pressure of 760 mmHg is called 1 atmosphere.
If a gas is said to be at standard temperature and pressure, s.t.p. (or normal temperature and pressure,
n.t.p.), this means it is at 760 mmHg and 0°C.

58
 = 760 mm

Atmospheric
pressure

Figure 5.1: A mercury barometer for measuring atmospheric pressure.

Another instrument used in measuring pressure of gases is known as a manometer. A manometer is a

device used to measure the pressure of gases other than the atmospheric pressure. It measures gas
pressure as a difference in mercury column heights. If closed it measures the difference in column heights
and gives absolute gas pressure. The open manometer measures the difference in column heights and
gives difference between gas and atmospheric pressures.

Worked Example 5.1

The atmospheric pressure at the summit of Mt. Meru is 606 mmHg on a certain day. What is the pressure
in atm?
Answer
This is a conversion problem. In Table 3.2 we are given that:
760 torr = 1 atm
1torr = 1 mmHg 760 mmHg = 1 atm
606 mmHg
 1 atm = 0.797 atm
760 mmHg
EXERCISE 5.1

Convert 749 mmHg to atmospheres

59
5.3.3 Volume
Volume of a gas is the quantity of the three-dimensional space occupied by the gas molecules.
Common units of volume include litres, cubic metres (M3) and millimeters (mm3).
Volume is a function of state and is interdependent with other thermodynamic properties of gas such as
pressure and temperature.

The Standard Molar Volume is the volume occupied by one mole of any gas at STP. Remember that
"STP" is Standard Temperature and Pressure. Standard temperature is 0 ° C or 273 K; Standard pressure
is 1 atmosphere or 760 mm Hg (also called "torr"). 1 mole of any gas at STP occupies 22.4 liters of
volume.

5.3.4 Temperature

Generally, temperature is defined as the degree of hotness or coldness of a body. In gases, temperature is
a measure of the mean energy of motion, called kinetic energy, of the gas particles.

Temperature is measured in Celcius (° C) although other countries like U.S still use Fahrenheit (° F).

The SI unit for temperatute is Kelvin (K); remember, 0° C = 273K.

5.3.5 Number of Moles of a Gas

The mole is the unit of measurement in the International System of Units (SI) for amount of
substance. It is defined as the amount of a chemical substance that contains as many elementary
entities, e.g., atoms, molecules, ions, electrons, or protons, as there are atoms in 12 grams of
carbon-12 (12C).
For example one mole of CO2 gas has (12g x 1) + (16g x 2) = 44g
Therfore two moles of CO2 gas will be 88g and so on.

EXERCISE 5.2
1. Convert 0.875 atm to mmHg
2. Convert 745.0 mmHg to atm
3. Convert 0.955 atm to kPa
4. A gas sample has a pressure of 800.0 mmHg. What is the pressure of this gas
sample in atmospheres and in kilopascals
5. Convert 300K to Celcius scale
6. Convert -23° C to Kelvin scale
7. Determine the weight in kg of 0.75 moles of NO2 gas.

60
Lecture 6
Gas Laws

6.1 Introduction
In Lecture five, we discussed the various properties of gas. Now that we understand what the gas
properties are, we are in a position to find out how they relate to one another.

Gas laws are physical laws that describe the properties of gas and how they affect one another.

Learning Objectives
After studying this lecture you should be able to:

 State different gas laws, including the Boyle’s law; Charles and Gay-
Lussac’s law; Avogadro’s law; the ideal gas law and the Dalton’s law of
partial pressure.

 Use relationships of the gas properties obtained using the empirical gas
laws to solve stoichiometry problems involving gases.

 Explain the concept of partial pressure in mixtures of gases.

6.2 The Pressure-Volume Relationship: Boyle’s Law

Boyle’s investigated the pressure–volume relationship of a gas sample as early as year 1662. When
temperature and other factors are held constant, changing the pressure of a gas causes an inverse change
in its volume and vice versa. After working with several gases and coming to the same findings, Boyle was
able to state a principle. To honour him the principle is called by his name.

Boyle's Law states that for a given sample of gas at constant temperature,
volume (V) is inversely proportional to pressure (P) and vice-versa.
Mathematically, PV = k’, where k’ is a constant

Experiment Boyle’s law

To get a feel for Boyle's Law, visualize a small balloon between your hands. The balloon is so small that
you can push all sides of it together between your hands without any of the balloon pouching out at any
point. When you push your hands together, the volume of the gas in the balloon decreases as the pressure
increases. When you let up on the pressure the volume increases as the pressure decreases.
When two variables are inversely proportional, like pressure and volume in the example above, the
product of the two variables will always remain constant.

61
That is P1V1 = k’ P2V2 = k’
Therefore: P1V1 = P2V2 = k’
Note: The value of the constant changes if the mass of gas or temperature changes.

Worked example 6.1

A sample of gas collected in a 350 cm3 container exerts a pressure of 103 kPa. What would be the volume
of this gas at 150 kPa of pressure? (Assume that the temperature remains constant)

Answer
We use the relation P1V1 = P2V2
Given V1 = 350 cm3
P1 = 103 kPa
P2 = 150 kPa
V2 = ?

We rearrange the relation to solve for V2

P1 V1
V2 
P2
103 kPa  350 cm 3
  240 cm 3
150 kPa
The new volume is 240 cm3

Worked example 6.2

A sample of neon has a volume of 239 cm3 at 2.00 atm of pressure. What would the pressure have to be
in order for the gas to have a volume of 5.00 x 10 2 cm3?
We use the same relation P1V1 = P2V2

We are given P1 = 2.00 atm

V1 = 239 cm3
V2 = 5.00 x 102 cm3
P2 = ?

Let us rearrange the relation to solve for P2

P1 V1 2.00 atm  239 cm 3
P2    0.956 atm
V2 5.00  10 2 cm 3
The new pressure is 0.956 atm.

6.3 The Temperature-Volume Relationship: Charles’ and Gay-

Lussa’s Laws
In their studies they showed that, at constant pressure, the volume of a gas sample expands when heated
and contracts when cooled. The quantitative relations involved in changes in gas temperature and volume
turn out to be remarkably consistent. This led to the formation of the law:

62
 Charles’s law states that the volume of a gas is directly proportional to the
temperature of the gas, provided the amount of gas and pressure are held constant
V
Mathematically:  k, where k is a constant
T

6.3.1 Experiment on Temperature-Volume Relationship

We will measure the temperature (T) with a thermometer calibrated in Celcius and a ballon filled with
helium gas to a volume of 3.000 L at room temperature (20.00 oC). We will vary temperature and observe
what happens to the volume of the gas. The data below was collected. A graph was drawn of volume
verses temperature and is shown as
Figure 6.1
Table 6.1: Relationship of temperature and volume of a gas
Temperature in oC Volume in litres
20.00 3.000
30.00 3.102
8.00 2.877
0.00 2.795

A graph helps us visualize the changes taking place with change in temperature.

Volume verses Temperature

3.15

3.1

3.05

3
Volume in Litres

Volume
2.95
Linear (Volume)

2.9

2.85

2.8

2.75
0 5 10 15 20 25 30 35
Temperature in degrees Celcius

Figure 6.1: Volume (L) versus Temperature (oC)

The graph is a straight line with equation V = 0.0102T + 2.7951

This result and those from literature have revealed that at any given pressure the plot of volume versus
temperature yields a straight line. When the line is interpolated to zero volume, the intercept on the
temperature axis (x-axis) is -273.15 oC. Lord Kelvin identified -273.15 oC as the absolute zero,

63
theoretically the lowest attainable temperature. The relation of Kelvin and Celsius temperature scale is as
follows:

Table 6.2: Comparison between Kelvin scale and Celsius scale

Kelvin Scale (K) Celsius Scale (oC)
Absolute zero 0 -273.15
Freezing point of water 273.15 0
Boiling point of water 373.15 100

We can convert Celsius to Kelvin as follows:

K = (oC + 273.15 oC)
V V1
We have shown that:  k . If the variables are labeled as  k for the first condition and
T T1
V2
written as  k at another condition, k is the same constant therefore:
T2
V1 V2

T1 T2
Worked Example 6.3
A balloon is filled with methane until it has a radius of 10 cm at room temperature (20.00 oC). It is then
placed in an incubator and heated to 50.00 oC. What will be the volume and the balloon radius at 50.00
oC? Assume all other factors constant.

Answer
Do you remember how to calculate the volume of a sphere?
Use the following equation: V = 4 π r
3
3
V1 = (4/3)r13 = (4/3) (3.1415) (10 cm)3 = 4189 cm3
From the relation V1/T1 = V2/T2
Let us rearrange and solve for V2
V1
V2 =  T2
T1
V2 = (4189 cm3) (323.15 K)/(293.15 K) = 4618.0 cm3
The final volume is 4618.0 cm3
To find the new radius we use V = 4/3  r3
Let us rearrange and solve for r3:
r3 = V/4/3  = (4618 x3)/4 x 3.1415 = 1102 cm3
r= 3
1102 cm 3 = 10.33 cm
The final volume is 4618 cm3 and the new radius of the balloon is 10.33 cm

Worked example 6.4

A hydrogen gas thermometer has a volume of 150.0 cm3 when immersed in a mixture of ice and water
(0.00 oC). When immersed in boiling liquid ammonia, the volume of hydrogen, at the same pressure, is
131.7 cm3. Find the temperature of boiling ammonia on the Kelvin and Celcius scales.
Answer
Let us use the relation V1/T1 = V2/T2

64
Given: V1 = 150.0 cm3
T1 = 0.00 oC = 273.15 K
V2 = 131.7 cm3
T2 = ?
Solving for T2:
T2 = V2 x T1/ V1 = (131.7 cm3 x 273.15 K)/ 150.0 cm3 = 239.8 K
Temperature of boiling ammonia on the Celcius scale is 239.8 – 273.15 = -33.35 oC
The boiling temperature of ammonia is 239.8 K or -33.35 oC.

6.4 The Volume-Amount Relationship: Avogadro’s Law

Thus far we have concerned ourselves only with the volume (V) of a gas, its temperature (T), and its
pressure (P). We have ignored how much gas is present. At first glance, we might confuse volume with
quantity, or how much gas is present in a container. However, as we have seen, volume clearly can change
even though the amount of gas in a vessel remains constant. The best way to measure the amount of gas
present in a container is to measure its mass, because mass remains constant unless gas is added or
removed.

What is the relationship of mass and number of moles of a given

? gas/substance?

We recall from stoichiometry, mass is proportional to the number of moles of a substance that is present.
So in this study we will thus use moles as a measure of gas quantity.
Let us consider a container filled with 1 mol gas at a constant temperature and pressure (i.e. volume can
vary). The addition of 1 mol of gas (i.e. doubling of gas quantity) results in a two-fold volume change.
The addition of 3 mol gas (i.e. quadrupling of gas quantity) results in a four-fold volume change. Such
experiments were first performed by Amedeo Avogadro in 1811, and the following principle is named
Avogadro's Law in his honour:

Avogadro’s law states that at constant pressure and temperature, the volume of a
gas is directly proportional to the number of moles of the gas present.

Mathematically it is written as: V = nk” where n is moles of gas and k” is a constant.

Alternatively:
V1 V2

n1 n2
At STP the number of molecules contained in 22.4L of a gas is 6.02 x 10 23, that is 1 mole (mol.)

1 mole gas = 22.4 L gas (at STP)

65
6.5 The Ideal Gas Law
Now we are in the position to use the equations, which we have thus far discovered or proved to
combine into a single, powerful expression known as the Ideal Gas Law.

The Ideal Gas Law states that the pressure-volume product of a gas is
proportional to the amount of gas present in the sample and to the
temperature of the gas.

Mathematically, we write PV = nRT, where R is a constant known as the universal gas constant

6.5.1 Derivation of Ideal Gas Law

Since volume is proportional to both n (moles of gas) and to T (Kelvin temperature), we write V = rnT,
where r is a new constant. Since volume is inversely proportional to P (pressure), (Boyles law), we can
further write V = RnT / P, where R is a constant that incorporates r. Rearrangement yields PV = nRT.

The ideal gas law equation contains a constant R, the universal gas constant. Unlike the previous
constants, which can (but do not necessarily) differ from gas to gas and from situation to situation, R is
constant for all gases at all temperatures, pressures, volumes, and gas quantities. It takes several forms:

Useful values of R:
 8.314472J/(mol x K)
 8.314472 x 10-2(L x bar)/mol x K)
 8.205746 x 10-5(m3 x atm)/(mol x K)
 8.205746 x 10-2(L x atm)/(mol x K)

Note that the value of R given, temperature is always in Kelvin and quantity is always in moles. It is
important to be able to deduce which value of R should be implemented when solving an ideal gas
problem. R should be selected based on the units used in a problem and the units desired in the result.

Worked example 6.5

What is the volume occupied by 13.7g Cl 2 (g) at 45 oC and 745 mmHg?
Answer
Let us list down what we are given. Are the given items in the right units in order to calculate what we are
asked?
Given: PV = nRT
1atm
P = 745 mmHg, change into atm = 745mmHg x = 0.980 atm
760 mmHg
V=?
1 mol Cl 2
n = 13.7g Cl2, change into mol = 13.7g Cl2 x = 0.193 mol Cl2
70.91g Cl 2
R = 0.08206 L atm mol-1 K-1
T = 45 oC + 273.15 = 318.15 K

66
Rearrange the ideal gas equation, and solve for V to get:
nRT 0.193 mol  0.08206 L atm mol 1 K 1  318 K
V= = = 5.14 L
P 0.980 atm
The volume occupied is 5.14 L

Worked example 6.7

Find the number of atoms of He in a volume of 202,700 ft3 at 25.0 oC and 1 atm?
Here you need to remember the relationship between atoms and number of moles. Also note the units.
Given: PV = nRT
P = 1 atm
V = 202,700 ft3 = 5,739,824 L
n=?
R = 0.08205746 L atm mol-1K-1
T = 25.0 + 273.15 = 298.15 K

Rearrange the ideal gas law equation, and solve for n:

PV 1atm  5739824 L
n= = = 234629 mol He
RT 0.08205746 L atm mol 1 K 1  298.15 K

Using stoichiometry, we find that there are:

234629 mol x 6.022 x 1023 atoms mol-1 = 1.41 x 1029 atoms He

Worked example 6.8

A 12.8 L cylinder contains 35.8 g O2 at 46 oC. What is the pressure of this gas, in atmosphere?
Given: PV = nRT
V = 12.8 L
P=?
n = 35.8 g/31.9988 = 1.11879 mol
R = 0.08205746 L atm mol-1K-1
T = 46 oC + 273.15 = 319.15 K
Rearrange the ideal gas equation and solve for P:
nRT 1.11879 mol  0.08205746 L atm mol 1 K 1  319.15 K
P   = 2.29 atm
V 12.8 L
The pressure is 2.29 atm

Worked examples 6.9

What mass of ammonia would you get from enough nitrogen with 689 litres of hydrogen gas at 350 oC
and 4587 mmHg?
3H2 + N2 → 2NH3

Given: PV = nRT
V = 689 l H2,

67
 T = 350 oC + 273o = 623 K
n=?
P = 4587 mmHg = 6.0355 atm
R = 0.0821 L.atm/K.mol
6.0355 atm  689L
Find n = PV/RT = = 81.3 mol H2
L.atm
0.0821  623K
K.mol
From the equation the ratio of hydrogen to ammonia is 3:2
Therefore number of mols of ammonia is 81.3/3 x 2 = 54.2 mol
Using stoichiometry mass = mols x Fw = 54.2 x 28.016 = 1518.4672 g
The mass of ammonia is 1.518 kg

6.6 Gas Mixtures

What happens when gases are mixed in one container? Do they obey the
? gas laws?

So far, our discussion has been focused on unmixed gases (i.e. pure nitrogen gas). However, most gases
exist in mixtures (for example, the air is approximately 78.1% nitrogen, 20.9% oxygen, 0.9% argon, and
0.1% other). In order to find out the behaviour of gases in mixtures, we need define the gas mixture.
A gas mixture is nothing more than the sum of its components. There are two laws that make it possible
to “dissect” a gas mixture and analyze the component gases individually. Before studying and applying the
two laws some more definitions are needed.

The partial pressure of a component of an ideal gas mixture is equivalent to the pressure that the
component gas would possess if it alone occupied the volume of the gas mixture at the same temperature
as the mixture. The partial volume of a component of an ideal gas mixture is equivalent to the volume
that the component gas would occupy if it alone possessed the pressure of the gas mixture at the same
temperature as the mixture.

Dalton’s Law of Partial Pressures says that: The sum of all the partial pressures of
the gases, which behave ideally, in a volume is equal to the total pressure.
Alternatively: The pressure of a mixture of ideal gases is equal to the sum of the partial
pressures of the component gases.

Mathematically, if Pi is the partial pressure of the ith gas in a mixture of n ideal gases (with partial pressures
P1, P2, etc.), where Pm is the pressure of the gas mixture, then:

How are the partial pressures related to the total pressure? For example P1?

68
P1 n1 RT / V n1
  = X1
PT n1  n2  RT / V n1  n2
Where X1 is the mole fraction of gas no.1

The mole fraction (X1) is a dimensionless quantity that expresses the ratio of the
number of moles of one component to the number of moles of all components
present

Worked example 6.10

A mixture consists of 0.495 g of gas A of MW 66.0, and 0.182 g of a gas B of MW 45.5; the total pressure
is 76.2 cm of mercury. Calculate the partial pressures of the two gases.
Answer
n1
 X1
n  n2
Given: 1
Let us find the number of mols for each gas:
0.495
Gas A is  0.0075
66.0
0.182
Gas B is  0.0040
45.5
The total number of moles = 0.0075 + 0.0040 = 0.0115
The mole fraction of A is thus 0.0075/0.0115
0.0075
 76.2 cm of mercury
Partial pressure of A = 0.0115 = 49.7 cm of mercury
And
Partial pressure of B = 76.2 – 49.7 = 26.5 cm of mercury

Worked example 6.11

A volume of 125 mL of He measured at 0.60 atm, and 150 mL of Ne at a pressure of 0.80 atm, are passed
into a vessel whose capacity is 500 mL. What is the total pressure of the mixture in the vessel at the same
temperature?
Answer
The partial pressure pHe of He is the pressure the gas would exert if it alone occupied the 500 ml vessel;
since its pressure is 0.60 atm when it occupies 125 mL, it follows from Boyle’s law that:
PHe x 500 = 0.60 x 125
0.60  125
PHe  = 0.15 atm
500
Similarly:
PNe x 500 = 0.80 x 150
0.80  150
p Ne  = 0.24 atm
500
The total pressure is 0.15 + 0.24 = 0.39 atm

69
Things to remember when working gas related problems

 Know the units and dimensions of pressure, volume and temperature and how to convert them
to what you are asked.

 The gas laws require an absolute temperature, usually Kelvin, in the equations. Learn how to
convert any temperature measurement you are given to Kelvin. K = (oC + 273.15 oC) 1K/1 oC.

 Carefully label the dimension and condition of each variable. The dimensions of the same
condition must be labeled with the same subscript (e.g. P1, V1).

Summary
Gas is a state of matter that has no defined shape and no defined volume. Under
atmospheric conditions, a number of elemental substances are gases: hydrogen, nitrogen,
oxygen, ozone, fluorine, chlorine and the group 8A elements (the noble gases).
Gases exert pressure because their molecules move freely and collide with any surface in
their path. Gas pressure units include millimeters of mercury (mmHg), torr, pascals and
atmospheres. One atmosphere equals 760 mmHg, or 760 torr.
The pressure-volume relationships of ideal gases are governed by Boyle’s law: volume is
inversely proportional to pressure (at constant temperature and n). The temperature-
volume relationships of ideal gases are described by Charles’s and Gay-Lussac’s law:
Volume is directly proportional to temperature (at constant pressure and n). Absolute zero
(-273.15 oK) is the lowest theoretically attainable temperature. On the Kelvin temperature
scale, 0 K is absolute zero. In all gas law calculations, temperature must be expressed in
Kelvin. The amount-volume relationships of ideal gases are described by Avogadro’s law:
Equal volumes of gases contain equal numbers of molecules (at the same temperature and
pressure).
The ideal gas equation, PV = nRT, combines the laws of Boyle, Charles, and Avagadro.
This equation describes the behaviour of an ideal gas.
Dalton’s law of partial pressures states that in a mixture of gases each gas exerts the same
pressure as it would if it were alone and occupied the same volume.

Exercise
1. (a) List five compounds that are gases at room temperature.
(b) List five elements that are gases at room temperature.

70
2. Convert the atmospheric pressure of 750 mmHg to atm
3. Convert 0.875 atm to mmHg
4. Convert 745.0 mmHg to atm
5. Convert 0.955 atm to kPa
6. A gas sample has a pressure of 800.0 mmHg. What is the pressure of this gas sample in atmospheres
and in kilopascals
7. Convert 300K to Celcius scale
8. Convert -23° C to Kelvin scale
9. Determine the weight in kg of 0.75 moles of NO2 gas.
10. A sample of gas collected in a 350 cm3 container exerts a pressure of 103 kPa. What would be the
volume of this gas at 150 kPa of pressure and constant temperature?
11. A sample of neon gas has a volume of 500 cm3 at 2.00 atm of pressure. What would the pressure be
in order for the gas to have a volume of 5.00 x 10 2 cm3?
12. A hydrogen gas t has a volume of 250.0 cm3 at 0.00 oC. When the temperature is increased at the
same pressure, the volume of hydrogen is reduced to 150 cm3. Find the new temperature of of the
gas in the Kelvin and Celcius scales.
13. 2.00 g of hydrogen gas and 19.2 g of oxygen gas are placed in a 100.0 L container. These gases react
to form H2O(g). The temperature is 38 oC at the end of the reaction.
14. a) What is the pressure at the conclusion of the reaction?
b) If the temperature was raised to 77oC, what would the new pressure be in the same container?
15. Two moles of oxygen and one mole of nitrogen are contained in a cylinder with a volume of 10.0L at
298K. What is the total pressure? What is the partial pressure of oxygen?
16. An automobile tire is inflated to 3.0 atmospheres indoors at a temperature of 302 Kelvin. The tire is
then moved outside, where the temperature is 261 Kelvin. Given this data and assuming that the
volume of the tire does not change, what will be the resulting pressure in the tire?

References
1. Chang, R., General Chemistry, 3rd Edition, Random house Inc., New York. 2000.

2. Hill, J.W., Chemistry for Changing Times, 5th Edition, Macmillan Publishing Company,
New York, 1988.

3. Petrucci, R. H., Harwood, W. S., Herring, G.E. and Madura, J. (2006) General Chemistry:
Principles and Modern Application, 9 th Edition. Prentice Hall

71
Lecture 7
Qualitative Inorganic Analysis

7.1 Introduction
Qualitative analysis of an inorganic mixture involves the detection of the anions and the cations present in
a sample of a substance, a mixture of substances, or solution. In this lecture you will study the classical
methods of qualitative analysis. These can be broadly divided into two categories - dry tests and wet tests.
Dry tests are performed on solid samples and usually at high temperatures while wet tests are performed
on solutions.
The study of qualitative inorganic analysis is invaluable for every student of chemistry because this is
where the student comes across and handles various materials, which are studied in theory courses. Also,
it provides the students an excellent opportunity of learning by doing the chemistry of elements and the
application of a variety of chemical phenomena, such as solution equilibria, solubility-product equilibria,
buffers, acid-base reactions, acid-base equilibria and oxidation-reduction reactions.

Learning Objectives
After studying this lecture you should be able to:
 Describe the principles involved in the qualitative analysis of a mixture of
inorganic salts
 Explain how to detect the presence of the anions and cations in a mixture of
inorganic salts,
 Associate colours formed during flame tests with certain cations present in a
mixture of inorganic salts,
 Use the selective precipitation to form analytical groups of cations
 Write chemical equations for the tests for the anions and the cations present in
a mixture of inorganic salts,
 Explain the chemistry of various tests for anions and cations,
 Explain the application of solubility product data in classification and analysis
of cations
 Remove interfering anions from a mixture.

7.2 Analysis of Anions

We will begin with the identification and analysis of anions. It is appropriate to elucidate for the anions
first as this might help in the analysis for cations.

You are in the laboratory and you are given an unknown solid sample. How
? would you proceed in analyzing it?

72
7.2.1 Classification of the Anions
For the systematic identification of the anions present in any mixture, we will divide them into three
classes:

Class I anions
The anions of this class evolve gases or vapours on treatment with dilute HCI or H 2SO4. These are
anions of weak acids namely carbonates, sulphites, sulphides, thiosulphates, nitrites and acetates.

Class II anions
The anions of class II evolve gases or vapours on treatment with conc. HCl or conc. H 2SO4. These
anions are fluorides, chlorides, bromides, iodides, nitrates and oxalates.

Class III anions

The anions of this class do not evolve any gas on treatment with acids. These are identified by formation
of precipitate on treatment with certain reagents. Sulphates, borates and phosphates ions are the anions of
class III.

Note: The classes are formed according to the reactivity towards certain reagents. It is not always
necessary to test for the presence of anions of class I before testing for the presence of anions of class II
or class III in any mixture. They are provided as a good guidance in the laboratory.
Anions of class I and II can easily be shown to be present in the mixture by performing some preliminary
tests

7.2.1.1 Preliminary Tests for the Anions of Class I

When you are confronted with an unknown sample, add dilute hydrochloric or sulphuric acid to a few
grams of the dry mixture, if a gas is evolved, the colour and odour should help to draw inference as
shown in Table 7.1. Heat the test tube if necessary. If no gas is evolved, anions of this class are absent in
the mixture.

Table 7.1: Preliminary Tests for the Anions of Class I

No. Observation Inference Explanation/ Reaction
1. Colourless gas CO32- may CO32-(aq) + 2H+(aq) CO2(g) + H2O(l)
evolved with brisk be present Ca(OH)2(aq) + CO2(g)  CaCO3(s) + H2O(l)
effervescence. On
passing the gas in
lime water, it turns
milky.
2. Colourless, SO32- may SO32- + H+ (aq)  H2O(l) + SO2 (g)
suffocating gas with be present
Cr2O72- (aq) + 2H+ (aq) + 3SO2(g) 
smell of burning
sulphur; the gas 2Cr3+ (aq) + 3SO42- (aq) + H2O(l)
turns acidified (green)
K2Cr2 O7 paper
green.

73
 3. Colourless, S2O32- may S2O32- (aq) + 2H+(aq)  2O(l)+ SO2(g) +
suffocating gas with be present S(S)
smell of burning
sulphur and there is
a deposit of sulphur
in the test tube. The
gas turns acidified
K2Cr2O7 paper
green.
4. Colourless, gas with S2- may be S2- (aq) + 2H+ (aq)  H2S(g)
smell of rotten eggs, present Pb2+ (aq) + H2S(g)  PbS(s) + 2H+(aq)
turns moistened
(black)
lead acetate paper
black.
5. Light brown gas NO2- may 2NO2-(aq) + 2H+ (aq)  H2O(l) + NO(g) +
which turns KI- be present NO2(g)
starch paper blue.

6. Colourless vapours CH3COO- CH3COO-(aq) + H+(aq)  3COOH(g)

with smell of may be
vinegar on warming present
the test tube

7.2.2.1 Preliminary Tests for the Anions of Class II

Reaction of the solid sample towards concentrated sulphuric acid in a dry test tube will show the presence
or not of class II anions. Observe the reaction at room temperature and then warm the test tube gently. If
no gas or vapours are evolved, the anions of this class are absent. Table 7.2 should be used when drawing
inferences.

Table 7.2: Preliminary Tests for the Anions of Class II

No. Observation. Inference Explanation/Reaction

74
 1. Colourless, pungent Cl- may be Cl- (aq) + H aq)  HCI(g)
+

smelling gas is evolved, present

which gives white dense HCI(g) + NH3(g)  NH4Cl(g)
fumes of NH4Cl when a
glass rod dipped in
aqueous ammonia is
placed in the evolved gas.
2. Reddish brown gas is Br- may be Br- (aq) + 6H+ (aq) + 3SO42-
evolved and the solution present
(aq)  2HSO4-(aq) + SO2(g) + Br2(g)
in the test tube acquires a
yellow-red colour. +2H2O(l)

3. Violet vapours of I2 are I- may be 2I- (aq) + 6H+(aq) + 3SO 42- (aq) 
evolved, which turn the present 2HSO4-(aq) + SO2(g) + I2(g) + 2H2O(l)
moist starch paper blue.

4. Oil drops inside the test F- may be 2F-(aq) + 2H+ (aq)  2HF(g)
tube and the pungent present
smelling gas leaves a
white deposit on a
moistened glass rod.
5. Pungent smelling, brown NO3- may be NO3- (aq) + H+(aq)  HNO3(aq)
fumes of NO2 are present 4HNO3(aq)  4NO2(g) + O2(g) +
evolved. The evolution
2H2O(l)
of NO2 increases on
Cu(s) + 4HNO3(aq) 
heating the reaction
mixture with copper Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
turnings.
6. Colourless, odourless gas 2- 2-
C2O4 may be C2O4 (aq) + 2H (aq
+
 CO(g) +
is evolved which turns present CO2(g) + H2O(1)
lime-water milky and
Ca(OH)2(aq) + CO2(g)  CaCO3((s) +
burns with a blue flame.
H2O(l)
CO(g)+ O2(g)  CO2(g)

7.2.2 Confirmatory Tests for the Anions

The preliminary tests described in the preceding sub-section do not always offer very conclusive evidence
for the presence of anions in a mixture. Therefore, further tests have to be performed for confirmation of
those anions, which are indicated by the preliminary tests and for the detection and confirmation of the
anions of Class III, which have no preliminary tests. The following tests are performed on the solution of
anions and are confirmatory.

75
In general tests for anions should be carried out on sodium salts. Why? It is a common practice to fuse
the unknown compound (which is likely not to be a sodium salt) with moist, solid sodium carbonate for
15 minutes. This converts at least some of the unknown substance to its sodium salt. If the resulting mass
is then diluted with distilled water and then filtered to produce a filtrate containing sodium salt. However,
all common acetates, nitrites, nitrates and thiosulphates are soluble in water. Confirmatory tests for these
anions can be performed with the water extract of the mixture.
After preparation of the water extract or the sodium carbonate extract, the following tests are performed
to confirm the presence of various anions in the mixture.
Sulphide ions: are confirmed by reaction of sodium nitroprusside or lead acetate with a sodium
carbonate extract in a test tube. A purple/violet colour or black precipitate confirms sulphide ions
respectively:
S2-(aq) + [Fe(CN)5NO]2-(aq)  [Fe(CN)5NOS]4- (aq) purple or violet colour
S2- (aq) + Pb2+(aq) PbS(s) black

Sulphite ions: A sodium carbonate extract is employed in confirming the presence of this ion in the
mixture. Any one of the following reagents; dilute HCl, acidic KMnO 4 and I2 can be used. However
certain ions may interfere with these tests.

What is an interfering ion/radical

?
An ion/radical, which participates in a reaction, which, is not intended for it, interferes with the analysis
of the intended ions.

For best results of the intended ion, the interfering ions must be removed first from the mixture. This is
achieved by adding BaCl2 solution to it. If a white precipitate appears it may be due to the presence of
SO32- , SO42- or excess of CO32- ions in the solution. The precipitate is filtered and divided into three
parts.

(i). To the first part, dilute HCl is added. Evolution of SO 2, gas which turns acidified dichromate paper
green confirms the presence of SO32- ions:

BaSO3(s) + 2H+ (aq)  2+

(aq) + SO2(g) + H2O(l)

(ii) To the second part, a few drops of acidic KMnO4 solution are added. If the pink colour of KMn0 4 is
discharged, the presence of SO32- ions is confirmed:

5BaSO3(s) + 2MnO4- (aq) + 6H (aq)  5BaSO4(s) + 2Mn (aq) + 3H2O(l)

+ 2+

(iii) To the third part, an I2 solution is added. If colour of iodine is discharged, SO32- is confirmed:

BaSO3(s) + I2(aq) + H2O(l)  BaSO4(s) + 2HI(aq)

Thiosulphate ions: are also confirmed by using the sodium carbonate extract. Two reagents can be
employed in this case; these are dilute H2SO4 and acidic (acetic acid) AgNO3 solution.

76
Evolution of SO2 accompanied by a yellow precipitate of sulphur confirms the presence of thiosulphate
ions:
S O 2-(aq)+ 2H+ (aq)  SO (g) + S(s) + H O(l)
2 3 2 2
and formation of white precipitate which turns yellow, orange-brown and finally black in quick succession
confirms the presence of thiosulphate ions:
S2O32- (aq) + 2Ag+ (aq)  Ag2S2O3(s)
Ag2S2O3(s) + H2O(l)  Ag2S(s) + 2H+(aq) + SO42-(aq)
Black

Nitrite ions: are soluble in water hence we employ the water extract in their confirmation. Three reagents
can also confirm their presence.
(i) Appearance of a brown colour throughout the solution after addition of freshly prepared acidic 0.2 M
FeSO4 solution to the cooled water extract solution confirms the presence of nitrite ions:
NO - (aq) + CH COOH (aq)  HNO (aq) + CH COO- (aq)
2 3 2 3

3HNO2(aq)  3(aq) + H2O(l) + 2NO(g)

2+ 2+(
[Fe(H2O)6] (aq) + NO(g)  [Fe(H2O)5NO] aq) + H2O(l)

(ii) Add KI solution, starch solution and dilute H 2SO4.to a few ml of the water extract and if a deep blue
colour appears it confirms the presence of nitrite ions:
2NO2-(aq) + 4H (aq) + 2I- (aq)  2NO(g) + I2 (aq) + 2H2O(l)
+

I2(aq) + Starch  Blue coloured complex

(iii) A blood red colour formed after addition of acidic FeCl 3 solution confirms nitrite ions:
NO2-(aq) + H2NCSNH2(s)  N2(g) + CNS- (aq) + H2O(l)
Fe (aq) + 3CNS-(aq)  Fe(SCN)3(aq)
3+

(Blood red colour)

Note: the nitrite ion is a moderately strong oxidising agent in acidic medium. It oxidises
S2- to S,
SO32- to SO42-
S2O32- to SO42- + S
I- to I2
Therefore, these anions cannot be present if NO2- ions are present in the mixture.

Write the balanced chemical equations for the oxidation of interfering ions by
the nitrite ion in acidic medium.

Acetate ions: Either the solid mixture or the water extract can be used to confirm the presence of these
ions.
React a solid sample with warm acidic rectified spirit. If a pleasant, fruity odour is sensed, then ethyl
acetate is formed, This confirms the presence of acetate ions in the mixture:

77
 CH3COO-(aq) + H+(aq)  CH3COOH(aq)
CH 3 COOH aq   C 2 H 5 OHaq  H  CH 3 COOC 2 H 5 aq   H 2 Ol
2SO 4

What are the interfering ions in the confirmation of acetate ions when the water extract is
? employed?

If SO42- and PO43- ions are present, they will interfere with the test for acetate ions so they are removed
by precipitating with Ba(NO3)2 solution.

Now, add 0.1 M La(NO3)3 solution to the resulting filtrate and then add 0.01 M I2 solution drop wise till
the colour of I2 persists, after a minute, add one drop of 1 M aqueous ammonia. If a blue or blue-brown
ring is developed around the ammonia drop within a short time, presence of acetate ions is confirmed.
The ring probably develops due to the adsorption of iodine by basic lanthanum acetate.

Nitrate ions: The test for nitrate ion (brown ring test) is based on its ability to oxidise Fe2+ to Fe3+ in
acidic solution with the production of NO gas. Since NO is more soluble in water at low temperature, in
2+
well cooled solution it reacts with excess Fe present in solution to form brown nitrosyliron(II) complex
2+
ion, [Fe(H2O)5NO] . A brown ring forms at the zone of contact of the two liquids. Nitrite, bromide and
iodide ions interfere in this test.

NO3- (aq) + 4H+(aq) + 3Fe2+ (aq)  3Fe3+ (aq) + NO(g) + 2H2O(l)

[Fe(H2O)6]2+ (aq) + NO(g)  [Fe(H2O)5NO] 2+ (aq) + H2O(l)

Oxalate ions: We can confirm the acetate ions by a reaction of ammoniacal solution of CaC1 2 with
sodium extract solution. Formation of a white precipitate indicates the presence of oxalate ions.
2- 2+
C2O4 (aq) + Ca (aq)  CaC2O4(s)

If the precipitate dissolves in dilute H2SO4 and a warm solution dicolourizes KMnO4 solution with the
evolution of CO2 gas, the presence of oxalate ions is confirmed.
CaC2O4(s) + 2H+(aq)  H2C2O4 (aq) + Ca2+ (aq)
5H2C2O4 (aq) + 2MnO4-(aq) + 6H+(aq)  10CO2 (g) + 2Mn 2+ (aq) + 8H2O(l)

Chloride ion: are confirmed by the chromyl chloride test on a dry mixture. Also the solubility of AgCl
in aqueous ammonia formed from the sodium carbonate extract.
Cl-(aq) + Ag (aq)  AgCl(s)
+

AgCl(s) + 2NH3(aq)  Ag(NH3)2]+(aq) + C1- (aq)

4NaCl(s) + K2Cr2O7(s) + 3H2SO4(l)  2SO4(s) + 2Na2SO4(s) + CrO2Cl2(g) + H2O(l)

Chromyl chloride gas

78
 Pass the vapours in dilute NaOH solution a yellow solution will be obtained. Acidify the yellow solution
with acetic acid and then add lead acetate solution. Formation of a yellow precipitate of lead chromate,
which is soluble in NaOH, confirms the presence of chloride ions.
CrO2Cl2(g) + 4NaOH(aq)  Na2CrO4(aq) + 2NaCI(aq) + 2H2O(l)
Na2CrO4(aq) + Pb(CH3COO)2(aq)  PbCrO4(s) + 2CH3COONa(aq)

? What are the interfering ions in the chloride test?

The test fails if the mixture contains chlorides of Hg 2+, Sn2+, Pb2+ or Ag+.

Bromide ions: may be confirmed by using two procedures. The first procedure requires the acidification
of sodium carbonate extract with dilute HNO3 and boiling off CO2, then adding AgNO3 solution.
Formation of a light yellow precipitate which is partially soluble in aqueous ammonia solution, confirms
the presence of bromide ions:

Br-(aq) + Ag (aq)  AgBr(s) Light yellow precipitate.

+

The second procedure requires the acidification of the sodium carbonate extract with dilute HCI and
boiling off CO2. Then add carbon disulphide, dichloromethane or carbon tetrachloride. After that add
chlorine water drop-wise and shake. Bromide ions are oxidised to bromine, which imparts an orange
colour to the organic layer. This confirms the presence of bromide ions in the mixture.
2Br-(aq) + C1 (aq)  2CI- (aq) + Br (l)
2 2

Br2(l) + CS2(l)  Orange colour

Iodide ions: are confirmed by the same procedures as for the bromide above. To distinguish between the
- -
two ions (Br and I ) the colour of the AgI precipitate is pale yellow and the colour of the organic layer is
violet. The violet colour disappears on addition of excess of chlorine water. This confirms the presence of
iodide ions in the mixture:

I2(s) + C12(aq)  2ICl(aq)

Iodine mono-chloride (colourless)

Write the balanced equations for the two confirmatory

? procedures for Iodide ion?

Fluoride ions: Both the solid and the sodium carbonate extract are employed when confirming for the
fluoride ion.
To the powdered mixture, add an equal amount of sand and conc. H2SO4 in a dry test tube. Heat the test
tube, vapours of SiF4 will be given off. Hold a moistened glass rod in the vapours. Formation of a waxy
white deposit on the glass rod, confirms the presence of fluoride ions in the mixture.
4NaF(s) + SiO2(s)+ 4H2SO4(l)  SiF4 (g) + 4NaHSO4(s) + 2H2O (l)
3SiF4 (g) + 4H2O(l)  H4SiO4(s) + 2H2SiF6(aq)

79
 Silicic acid Hydrofluosilicic acid
(waxy white deposit)

-
Reaction of sodium carbonate extract with acidic CaC12 solution is used to show the presence of F ions.
-
If a white precipitate (CaF2) is formed it is an indication that F ions are present.
2F- (aq) + Ca2+ (aq)  CaF2(s)
If the precipitate dissolves in dilute H2SO4 and the warm solution does not discharged the pink colour of
KMnO4 it confirms the presence of fluoride ions in the mixture.

When the same procedure as for Fluoride ion was performed on a sodium
? carbonate extract the pink colour of KMnO4 was discharged with evolution of
a gas. What inference can you make?

So far we have discussed the confirmatory tests for the anions of class I and II, which are indicated by
preliminary tests with sulphuric acid. Now, we shall discuss the confirmatory tests for the anions of class
III, i.e., sulphate, phosphate and borate ions, which are not indicated by preliminary tests.

Sulphate ions: These ions are confirmed when a white precipitate, which is insoluble in concentrated
HCl and concentrated HNO3 is formed on the addition of acidified BaC1 2 solution.
SO42- (aq) + Ba2+ (aq)  4(s)

Phosphate ions: These ions are confirmed when there is a slow formation of a canary yellow precipitate
when ammonium molybdate solution is added to the sodium carbonate extract and gently warmed to 40
oC. The precipitate is soluble in ammonium acetate, aqueous ammonia and caustic alkali.
HPO42-(aq) + 3NH4+(aq) + 12MoO42-(aq) + 23H+(aq)  4)3[P(Mo3O10)4](s) + 12H2O(l)

Ammonium phosphomolybdate

Arsenate ion interferes in this test, as it also produces a similar yellow precipitate of ammonium
arsenomolybdate.
AsO43-(aq) + 3NH4+(aq) + 12MoO42-(aq) + 24H+(aq)  4)3[As(Mo3O10)4](s) + 12H2O(l)

? How would you distinguish between phosphate and arsenate ions?

Both ammonium phosphomolybdate and ammonium arsenomolybdate dissolve on boiling with

ammonium acetate solution, but only ammonium arsenomolybdate yields a white precipitate on cooling.

Borate ions: The test for borate ions is based on the reaction of borate ions with methanol in presence of
concentrated sulphuric acid, which acts as a dehydrating agent. On heating volatile methyl borate is
formed, which burns with a green edged flame. This confirms the presence of borate ions:

+
BO33- (aq) + 3H (aq) + 3CH3OH (l)  B(OCH3)3(g) + 3H2O(l)

80
 2B(OCH3)3(g) + 9O2(g)  B2O3(s) + 6CO2(g) + 9H2O(l)

2+ 2+
Note: Isolate the vapours from the mixture before burning otherwise Ba and Cu salts interfere
because these salts also impart a green colour to the alcohol flame.

7.2.3 Removal of Interfering Anions

As pointed above, an ion which participates in a reaction, which is not intended for it, interferes with the
analysis of the intended ions. In order to get valid results the interfering ions must be removed before the
analysis can be performed.

List the anions, which interfere with the analysis of cations of group
? III-VI

Removal of oxalate ions

Oxalate ions can be removed by repeatedly evaporating the solid mixture or the filtrate of Group II with
concentrated nitric acid to near dryness. This process is repeated several times until the residue gives a
negative test for the oxalate ions. Nitric acid oxidises the oxalate ions to CO 2 and water.
C O42-(aq) + 2NO - (aq) + 4H+ (aq)  2CO (g) + 2NO (g) + 2H O(l)
2 3 2 2 2

Note: Do not heat the residue to complete dryness because iron (III) oxide,
chromium (III) oxide and aluminium (III) oxide are rendered insoluble.

Removal of fluoride ions

Fluoride ions can be removed by repeatedly evaporating the dry mixture or the filtrate of Group II with
concentrated HCl in a china dish. Fluoride ions are volatilised off as hydrofluoric acid:

F- (aq) + H+ (aq)  HF(g)

Removal of borate ions

Borate ions are volatilised off as methyl or ethyl borate:
BO33- (aq) + 3CH3OH(aq) +3H+(aq)  B(OCH3)3(g) + 3H2O(l)

Removal of phosphate ions

Removal of phosphate ions is based on the fact that zirconyl phosphate, ZrO(HP0 4)2 is precipitated
from a solution containing hydrochloric acid ≤ 1 M concentration.
HPO42- (aq) + ZrO2+ (aq)  4)2 (s)
The precipitate is of variable composition depending on the concentrations of ZrO 2+', PO43- and H+
ions. Species like Zr(HPO4)2 , ZrPO4 and ZrO(H2PO4)2 may be formed.

81
7.3 Analysis of Cations
In the previous part; we have learnt the tests for detection and identification of individual anions, which
may be present in an inorganic mixture. In this section we will learn how to detect and identify cations.
For cations colour can be used as a preliminary test. This is possible because cations of some metals in
solution can be detected by colur while for some the flame test is applicable to dry mixtures.

7.3.1 Colour
Many transition metal compounds are coloured and this may give some indication of a metal present in
the mixture:

Table 7.3: Coloured transition metal compounds

Colour Ions
Blue Cu2+, Ni2+
Green Cu2+, Ni2+, Fe2+, Cr3+
Yellow Fe3+, CrO42-
Orange Cr2O72-

Purple MnO4-

7.3.2 Flame Tests

Flame tests can be useful for indicating the presence of Group I and group II elements:

Table 7.4: Colour emitted by group I & II elements during flame tests
Colour Ion
Persistent orange yellow Na+
Lilac (rose coloured when viewed K+
through cobalt glass)
Red Ca2+, Sr2+, Li+
Apple green Ba2+
Blue green Cu2+
Blue Pb2+

7.3.3 Application of the Solubility Product Principle

Appearance and flame tests are applicable to a few cations. To cater for more cations we will use the
solubility product principle. The principle is best employed in aqueous solution. There are two distinctly
different ways of classifying the metals into groups, according to:

82
 1. The periodic table grouping, which reflect similarities and differences in electronic
structures and gradations in physical and chemical properties.
2. The way in which the metals are associated in their systematic identification, or
qualitative analysis. It depends upon the solubilities of the various salts formed by the
metals

There are some twenty common cations that can be analyzed readily in aqueous solution. These cations
can be divided into five groups, according to the solubility products of their insoluble salts (Table 3).
Since an unknown solution may contain any one or all twenty ions, any analysis must be carried out
systematically from group 1 through group 5.
We will outline the procedure for separating these twenty ions by adding precipitating reagents to an
unknown solution and then give a short discussion of how each cation can be identified within its group.

Things to remember on solubility of salts in aqueous media:

The solubility of an ionic salt depends both upon its cations and its anions, but for simple
salts in aqueous solution at room temperature the following general observations are
useful.
Soluble compounds
 all salts of alkali metal ions and the NH4+ ion
 all salts of NO2-, NO3-, CH3CO2-, ClO3-, ClO4-, S2O32- ions
 most salts of Cl-, Br-, and I- ions except Ag+, Pb2+, and Hg2+ salts
 most salts of the SO42- ion except Sr2+, Ba2+, and Pb2+ salts
Insoluble compounds
most salts of CO32-, PO43-, OH-, O2-, and S2- ions except alkali metal and NH4+ salts

Group 1 cations: Excess dilute HC1 is added to the unknown solution. Only the Ag +, Hg2+, and Pb2+
ions precipitate as insoluble chlorides. All other ions form soluble chlorides remain in solution. It is
important to add enough HCI to the unknown solution to remove all the group 1 cations. If not
completely removed they will precipitate with the group 2 cations as insoluble sulfides; this would
interfere with further chemical analysis and lead to erroneous conclusions.

Group 2 cations: After the chloride precipitates have been removed by filtration, hydrogen sulfide is
reacted with the unknown solution, which now contains hydrochloric acid. H 2S is a diprotic acid;
therefore
H S (aq)
2 H+(aq) + HS-(aq) Ka1 = 5.7 x 10-8
HS-(aq)
+
H (aq) + S2- (aq) Ka2 = 1.2 x 10-13

The small values of the acid ionization constants mean that the sulfide ion concentration in solution is
very low. Moreover, the H+ ions supplied by the HCl in solution produce a common ion effect, which
further decreases the S2- ion concentration. (According to Le Chatelier's principle, the presence of
additional H+ ions will drive the above equilibria from right to the left). The extremely low sulfide ion

83
concentration in solution means that only those metal sulfides with the smallest K sp values will
precipitate out of solution, namely, Bi 2S3, CdS, CuS, and SnS (see Table 3). These precipitates are
removed from the solution by filtration.

? Recall the Le Chatelier’s Principle.

Table 7.5: Separation of cations into groups according to their precipitating reactions to various
reagents
Group Cation Precipitating Insoluble Ksp
reagents salt
1. Ag+ HCl AgCl 1.6 x 10-10
Hg2+ HgCl2 3.5 x 10-18
Pb2+ PbCl2 2.4 x 10-4

2. Bi3+ H2 S Bi2S3 1.6 x 10-72

Cd2+ in acidic CdS 1.4 x 10-28
Cu2+ solution CuS 1.0 x 10-44
Sn2+ SnS 1.0 x 10-26
3. Al3+ H2 S Al(OH)3 1.8 x 10-33
Co2+ in basic CoS 4.0 x 10-21
Cr3+ solution Cr(OH)3 3.0 x 10-29
Fe2+ FeS 3.7 x 10-19
Mn2+ MnS 1.4 x 10-15
Ni2+ NiS 1.4 x 10-24
Zn2+ ZnS 1.2 x 1023
4. Ba2+ Na2CO3 BaCO3 8.1 x 10-9
Ca2+ CaCO3 8.7 x 10-9
Sr2+ SrCO3 1.6 x 10-9
5. K+ no precipitating None
Na+ reagent "
NH4+ "

Group 3 cations: At this stage, the solution is made alkaline by addition of sodium hydroxide. In the
presence of excess OH- ions, ionization of H2S and HS- shifts from left to right and, hence, the
concentration of the S2- ions increases. Consequently
[M2+][S2-] > Ksp

Where M2+ represents the metal cations (Co2+, Fe2+, Mn2+, Ni2+ and Zn2+) Therefore, the sulfides of
these metals will precipitate out of solution. Note that the Al 3+ and Cr3+ ions actually precipitate as the

84
hydroxides Al(OH)3 and Cr(OH)3, rather than the sulfides, because the hydroxides are less soluble. The
solution is then filtered to remove the insoluble sulfides and hydroxides.

(1) Write solubility product expressions for saturated solutions of Ag 2CO3 and
Bi2S3
(2) Both Cu2+ and Co2+ form a precipitate on reaction with H2S, then why do they
belong to two different analytical groups?

Group 4 cations: Sodium carbonate is added to the basic solution. Normally, carbonate ions have a
tendency to hydrolyze in pure water, according to the equation
CO32- (aq) + H2O(l) HCO3- (aq) + OH- (aq)
and since most bicarbonate salts are soluble, no metal ions precipitate out of the solution. However, in
the basic solution, the excess OH- ions drive the equilibrium from right to the left (Le Chatelier's
Principle) and the increase in the CO32- ion concentration results in the precipitation of the insoluble
carbonates BaCO3, CaCO3, and SrCO3. These precipitates are removed by filtration.

It is advised that ammonium carbonate rather than sodium carbonate should be

? used to precipitate group IV cations. Why?

Group 5 cations: At this stage, the only cations possibly remaining in solution are Na +, K+, and NH4+.
The presence of NH4+ can be determined by adding sodium hydroxide:
NaOH (aq) + NH4+ (aq)  Na+ (aq) + H2O(1) + NH3(g)
The ammonia gas is detected either by its characteristic odour or by observing a piece of wet red litmus
paper turning blue when placed above (not in contact with) the solution. To confirm the presence of Na +
and K+ ions, we usually use a flame test (Table 4.4).

Note: Do not confuse the groups in Table 4.5 which are based on solubility
products, with those of the periodic table, which are based on the electron
configurations of the elements.

The separation of metal ions is represented in the form of a flow chart shown as Figure 7.1. Two points
regarding qualitative analysis must be mentioned. First, the separation of the cations into groups is made
as selective as possible; that is, the chosen anions added must be such that they will precipitate the fewest
types of cations. For example, all the cations in group1 form insoluble sulfides. Thus, if H 2S is reacted
with the solution at the start, as many as seven different sulfides might precipitate out of solution (group
1 and group 2 sulfides). This is an undesirable outcome. Second, the separation of cations at each step
must be carried out as completely as possible.

85
 Solution containing
ions of all cations

+ HCl

Group 1 precipitate
Filtration AgCl, HgCl2, PbCl2

Solution containing
ions of remaining
groups

+ H2S acidic
Group 2 precipitate
Filtration CuS, CdS, SnS, Bi2S3

Solution containing
ions of remaining
groups

+ NaOH
Group 3 precipitate
Filtration CoS, FeS, MnS, NiS,
ZnS, Al(OH)3, Cr(OH)3

Solution containing
ions of remaining
groups

+ Na2CO3
Group 4 precipitate
Filtration BaCO3, CaCO3, SrCO3

Solution containing
Na+, K+ and NH4+

Figure 7.1: A flow chart for the separation of cations in qualitative analysis

7.4 Separation of Individual Ions

The ions of the analysis scheme have been separated into five groups, each group of ions is further
subdivided. In some instances individual ions are obtained; in other cases, small subdivisions consisting of
several ions result. The techniques used in these separations include selective dissolution of a portion of a
group precipitate, complete dissolution of a group precipitate followed by selective precipitation of one or
more members of the group, and dissolution by formation of a complex ion. Examples of each type of
separation will be discussed.

86
7.4.1 Selective Dissolution
The separation of lead chloride from silver chloride and mercury(l) chloride during the analysis of Group
I is an interesting example of selective dissolution. The solubility product of lead chloride increases with
temperature, and the molar solubility of lead chloride is about three times greater in hot water than in
cold water. The solubilities of silver chloride and mercury(l) chloride do not change significantly with
temperature (hot water to cold water). Thus lead chloride dissolves selectively in hot water and can be
separated from a mixture of the Group I chlorides.

The sulfides and hydroxides of Group III can be separated into two subdivisions by selective dissolution
in 1 M hydrochloric acid. The sulfides of cobalt (II) and nickel(II) will not precipitate from acidic
solution, but once they precipitate from basic solution, the initial crystalline form of these sulfides (the
form) changes rapidly into a crystalline modification (the
FeS, ZnS, Al(OH)3, and Cr(OH)3, each of which is soluble in acid, can be separated from CoS and NiS,
which are insoluble in hydrochloric acid.

7.4.2 Dissolution Followed by Selective Precipitation

The separation of lead in Group II is an example of dissolution of a set of precipitates followed by
selective precipitation. Lead occurs in a set of four very insoluble sulfides, PbS, Bi 2S3, CuS, and CdS. In
order to dissolve these sulfides it is necessary to reduce the sulfide ion concentration in solution to zero
by oxidation of the sulfide ion to free sulfur. An excess of nitric acid is used as the oxidizing agent; when
this set of sulfides is heated with nitric acid, free sulfur and soluble nitrate salts are formed. A sample
equation (for the reaction of copper sulfide) is
3CuS + 8HNO3  3)2 + 3S + 2NO + 4H2O

Write and balance the equations for the formation of the nitrates of lead,
? bismuth, and cadmium from their sulfides.

Lead can be separated from the resulting solution of nitrate salts by precipitation of lead sulfate.
However, before lead sulfate is precipitated, the excess nitric acid in the solution must be removed,
because the sulfate ion is converted largely to hydrogen sulphate ion by hydrogen ions in high
concentration.

SO42-(aq) + H+(aq)  HSO4-(aq)

Under these conditions the concentration of sulfate ion is too low for the solubility product of lead
sulfate to be exceeded. The removal of the nitric acid is accomplished by adding sulfuric acid and
evaporating the solution to the point where sulfur trioxide fumes appear.

H2SO4  H2O + SO3

The more volatile nitric acid will have been expelled before the SO3 fumes appear. When the sulfuric acid
solution is diluted with water, sulfate ions are formed, and the lead precipitates as lead sulfate.

87
 Pb2+(aq) +SO42-(aq)  PbSO4(s)

Another example on complete dissolution followed by selective precipitation is the isolation of barium
ions from the group IV precipitate. In this case very careful control of the equilibrium concentration of
the precipitating agent (the chromate ion) is required. The group IV precipitate consists of the carbonates
of barium, strontium, and calcium. These carbonates dissolve readily in a solution of acetic acid. Barium
chromate is less soluble than strontium chromate and calcium chromate, so barium can be separated from
strontium and calcium in the solution.

The solubility products are 2 x 10-10 for BaCrO4 and 3.6 x 10-5 for SrCrO4. Calcium chromate is relatively
more soluble. The problem in this separation, then, is to control the concentration of the chromate ions
so that the concentration of the barium ion will be reduced to at least 0.0001 M and strontium chromate
will not be precipitated from a solution that is 0.1 M in the strontium ion. Let us first calculate the
concentration of chromate ion required to reduce the barium ion concentration to 0.0001 M.

[Ba2+][CrO42-] = 2 X 10-10

CrO 
2
4 
2  10 10

Ba 2  
2  10 10
1  10 4
 2  10 6 M

Now let us determine the maximum concentration of chromate ion that can be present without
precipitating any strontium chromate when the concentration of the strontium ion is 0.1 M

[Sr2+] [CrO42-] = 3.6 X 10-5

CrO 
2
4 
3.6  10 5

Sr 2  
3.6  10 5
0.1
 4  10  4 M

Thus we find that the concentration of the chromate ion must be held in the range of 2 x 10 -6 M and 4 x
10-4 M to cause a nearly complete precipitation of BaCrO 4 without precipitation of any SrCrO4. The
following equilibrium occurs in a solution containing chromate ions:

Cr2O72-(aq) + H2O(l) 2CrO42-(aq) + 2H+(aq)

Adjusting the hydrogen ion concentration can control the concentration of chromate ions in a solution
made by dissolving a dichromate salt in water. The equation for the equilibrium constant is

CrO  H 
2 2  2
 2.4  10 15
Cr O 
4
2
2 7

The chromate ion concentration is a function of the hydrogen ion concentration. The more acidic the
solution, the lower will be the chromate ion concentration; the more basic the solution, the higher will be
the chromate ion concentration. By substitution in the above expression, it can be shown that for a 0.01
M solution of dichromate ions, the hydrogen ion concentration must be adjusted to about 1 x 10-5 M (pH
= 5) to maintain the chromate ion concentration at about 5 x 10 -4 M. This concentration of chromate

88
ions is within the range (calculated above) necessary for the separation of Ba 2+ from Sr2+. A buffer
composed of acetic acid and ammonium acetate is used to maintain a pH = 5.

As chromate ions are removed from the system through precipitation of barium chromate, the
concentration of chromate does not change appreciably. This is because the excess of dichromate ions
serves as a reservoir for chromate ions, and as CrO42- is used in precipitating BaCrO4, the equilibrium

Cr2O72-(aq) + H2O(l) 2CrO42-(aq) + 2H+(aq)

shifts to the right and generates more CrO42-. The hydrogen ions that are formed unite with the acetate
ions of the buffer, and a constant pH is maintained.

7.5 Dissolution of Precipitates to form Complex Ions

Many precipitates in the qualitative analysis scheme dissolve, and the metal ions they contain can be
separated, because they form stable complex ions. Silver ion, for example, is separated from a mixture of
silver chloride and mercury (l) chloride by addition of ammonia. The diamminosilver (l) complex is
soluble.

AgCl(s) + 2NH3(g) Ag(NH3)+(aq) + Cl-(aq)

This equilibrium can be reversed, and silver chloride will re-precipitate if nitric acid is added to a solution
of the complex. The acid reacts with ammonia and reduces the concentration of free ammonia to such an
extent that the complex is no longer stable.
A second example of the use of complex ion formation to separate ions may be found in Group II.
Antimony and tin are separated from mercury(II) sulfide and arsenic(III) sulfide because antimony(III)
sulfide and tin(IV) sulfide react with hydrochloric acid and form the complex ions SbCl4- and SnCl62-,
respectively, but the mercury and arsenic compounds do not form complex ions under these conditions

How would you recover free ions of antimony (III) and tin (IV) from the
? complexes?

7.6 Confirmation Test for Ions

As the final step in the qualitative analysis of an ion, it is necessary to identify the ion by a confirmatory
test that is a reaction which is unique at that step in the scheme. The final steps involve identification by
complex ion formation, by oxidation-reduction, by precipitation of a coloured compound, or by an acid-
base reaction.

89
7.6.1 Identification Involving Formation of Complex Ions
The identification of cobalt, nickel, copper, and iron is based on the formation of colored complexes of
these ions. The complexes and their colors are summarized in table 7.6:

Table 7.6: Identification of some elements by formation of coloured complexes

Group Complex ion Colour
II 2+ blue
Cu (NH3)4
III 2- blue
Co (NCS)4
III Ni (DMG)2 red
III 2+ red
Fe (NCS)

In some cases complexes are formed in order to reduce the concentration of certain metal ions so as to
prevent their interference with the test for other metal ions. The formation of [Cu(CN) 2]- while
precipitating CdS is an example of such a use.

In general, the formation of complex ions is limited to ions of the transition metals and
the post-transition metals. Thus the use of complex ions is limited to the members of
analytical groups’ I-III, the groups that contain such metal ions.

7.6.2 Identification of Cations Using the Oxidation-Reduction Reactions

Oxidation-reduction reactions are used to confirm the presence of mercury(l), mercury(II), bismuth,
manganese, chromium, and tin. The reaction in Group I involving mercury(l) occurs when aqueous
ammonia is added to solid Hg2Cl2
Hg2Cl2(s) + NH3(aq)  2)Cl(aq) + NH4Cl(aq)

Mercury is both oxidized and reduced in this disproportionation reaction; elemental mercury (oxidation
number = 0) and mercury (II) are formed.

The other reactions involve the oxidation or reduction of the ion that is to be identified with a second
oxidizing or reducing agent. Bismuth is identified in Group II by the reduction of bismuth (III) to black
elemental bismuth in basic solution with a complex ion containing the tin(II) ion.
2Bi(OH)3(s) + 3[Sn(OH)3]-(aq) + 3OH-(aq)  2Bi(s) + 3[Sn(OH)6]2-(aq)
Tin is oxidized to tin (IV) during this reaction.

Chromium and manganese are identified in Group III by oxidation. The chromium (III) ion is oxidized
to the yellow chromate ion by hydrogen peroxide, whereas the manganese(II) ion requires BiO3-, a much
stronger oxidizing agent than hydrogen peroxide, to form the purple permanganate ion.

There is an interesting relationship between mercury and tin in Group II. If SnCl 3- is added to a solution
of Hg2+ in hydrochloric acid, Hg (black) or Hg2Cl2 (white) is formed.

90
 2[HgCl4]2-(aq) + [SnCl3]- (aq)  2Cl2(s) + [SnCl6]2-(aq) + 3Cl-(aq)

Hg2Cl2(s) + [SnCl6]2-(aq) + 3Cl-(aq)  2Hg(s) + [SnCl6]2-(aq)

Thus a solution of [HgCl4]2- can be used to test for the presence of tin(II) in an unknown sample, and a
solution of SnCl3]- can be used to test for mercury(II) in an unknown sample.

The metal ions of Analytical Groups IV and V exhibit no oxidation-reduction chemistry.

? Comment on this statement.

7.6.3 Identification by Precipitation

Many of the final confirmatory tests for the presence of the various ions in the qualitative analysis scheme
involve precipitation as the final test. Most of these tests are conclusive because the precipitate is the only
one that will form under conditions of the test or because only the ion being considered will give the
color of precipitate expected.

The following example illustrates these considerations

The confirmation of lead in Group I involves precipitation of yellow lead chromate. If the test solution
contains no lead ion and no contamination, no precipitate will form. If the solution contains no lead ion
but is contaminated with either silver or mercury(l) ions, a precipitate will form, but it will not be yellow.
A solution containing lead ion contaminated with silver or mercury(l) ion will give a precipitate that is not
yellow. A clean separation must be accomplished; the lead ion must be the only Group I ion in the
solution before a yellow precipitate can be obtained.

7.6.4 Identification by Acid-Base Reactions

Although many acid-base reactions are used to dissolve precipitates and to adjust conditions during the
course of an analysis, there is only one confirmatory test that can be considered to be a Bronsted acid-
base reaction; it is the identification of the ammonium ion. The ammonium ion is identified when it reacts
with a strong base and liberates ammonia.

NH4+(aq) + OH-(aq) (from a strong base)  NH3(g) + H2O(l)

If the reaction is warmed, gaseous ammonia is liberated and can be detected by its odour or by its
reaction with damp red litmus paper (red litmus turns blue in base).

Worked example 7.1

A solution contains the group 2 cation Sn2+ and the group 3 cation Fe2+, both at 0.10 M. The solution is
saturated with H2S ([H2S]= 0.10 M). Calculate the range of hydrogen ion concentrations that will result
only in the precipitation of Sn2+ ions as SnS.

91
Answer
Since the metal ion concentrations are fixed at 0.10 M, the precipitation of one ion and not the other
must be controlled by the ion concentration. Therefore, we need to calculate the sulfide ion
concentrations corresponding to the cation concentrations. For SnS.
Ksp = [Sn2+][S2-] = 1.0 x 10-26
1.0  1026
S 
2

0.10
 1.0  10
25
M
thus a sulfide ion concentration greater than 1.0 x 10 -25 M will result in the precipitation of SnS. For FeS
Ksp = [Fe2+][ S2-] = 3.7 x 10-19
3.7 1019
S 
2

0.10
 3.7  10
18
M
Thus a sulfide ion concentration greater than 3.7 x 10 -18 M will cause FeS to precipitation.

We know that the dissociation of H2S in aqueous media is reversible with the following equilibrium
relation
H2S(aq) 2H+(aq) + S2-(aq)
the equilibrium constant K is

K 
H  S 
 2 2
 6.8  10  21
H 2S
We can now calculate [H+] for each of the [S2-] values. For SnS we have

H  1.0  10 
 2  25
 6.8  10  21
0.10

H 
 2

6.8  10  21
1.0  10  25
 0.10

H 
 2
 6.8  10 3
H 

 82 M

+
The result shows that in order to prevent SnS from precipitating, [H ] must be equal to or greater than 82
M! Since no solution can have such a high acidity, SnS will precipitate no matter what the hydrogen ion
concentration may be.

For FeS

H  3.7 10 6.8 10

 2 18
 21

0.10
H  1.8 10
 2 4

H 0.013M


Thus, to prevent FeS from precipitating, the hydrogen ion concentration must be equal to or greater than
0.013 M.

92
Lecture 8
Acids and Bases

8.1 Introduction
Acids are important substances. They are used to remove rust and corrosion from metals, and as
electrolytes in wet cell batteries, such as sulphuric acid in a car battery. In humans and other animals, HCl
acid is part of the gastric acid secreted within the stomach to help hydrolyze proteins and polysaccharides
and other uses.

Learning Objectives

After studying this lecture you should be able to:

 Suggest simple tests you could carry out to determine if an unknown
substance is an acid or a base.
 State the chemical definitions of an acid and a base in terms of their
behaviour in water.
 Write the formula of the salt formed when a given acid and base are
combined.
 Explain the difference between the Arrhenius and Bronsted-Lowry
concepts of acids and bases, and give examples of an acid and a base in
which the Arrhenius concept is inapplicable.

8.2 Definitions of Acids

There are four common ways to define an acid:

 Arrhenius: an acid is a substance that increases the concentration of hydronium (H 3O+) ion when
dissolved in water, while bases are substances that increase the concentration of hydroxide (OH -) ions.

 Bronsted-Lowry: an acid is a proton (hydrogen nucleus) donor and a base is a proton acceptor.

 Solvent-system definition: an acid is a substance that, when dissolved in an autodissociating solvent,

increases the concentration of the solvonium cations, such as H 3O+ in water, NH4+ in liquid ammonia,
NO+ in liquid N2O4, SbCl2+ in SbCl3. Base is defined as the substance that increases the concentration
of the solvate anions, respectively OH-, NH2-, NO3-, or SbCl4-.

 Lewis: an acid is an electron-pair acceptor and a base is an electron-pair donor.

93
8.3 Theories of Acids and Bases
The Arrhenius theory of acids and bases

 Acids are substances which produce hydrogen ions in solution.

 Bases are substances which produce hydroxide ions in solution.

The Bronsted-Lowry theory of acids and bases

 An acid is a proton (hydrogen ion) donor.

 A base is a proton (hydrogen ion) acceptor.

8.3.1 The Relationship between the Bronsted-Lowry and the Arrhenius

Theories
The Bronsted-Lowry theory doesn't go against the Arrhenius theory in any way - it just adds to it.
Hydroxide ions are still bases because they accept hydrogen ions from acids and form water. An acid
produces hydrogen ions in solution because it reacts with the water molecules by giving a proton to them.
For example when hydrogen chloride gas dissolves in water to produce hydrochloric acid, the hydrogen
chloride molecule gives a proton (a hydrogen ion) to a water molecule. A co-ordinate (dative covalent)
bond is formed between one of the lone pairs on the oxygen and the hydrogen from the HCl.
Hydroxonium ions, H3O+, are produced.

+ -
H O H H O H Cl
Cl

H H

coordinate bond

H2O + HCl  H3O+ + Cl-

When an acid in solution reacts with a base, what is actually functioning as the acid is the hydroxonium
ion. For example, a proton is transferred from a hydroxonium ion to a hydroxide ion to make water.

H3O+(aq) + OH-(aq)  2H2O(l)

Showing the electrons, but leaving out the inner ones:

94
 + -

H H O O
O H O H

H H H H

This proton is ... to this

transfered lone pair

It is important to realise that whenever you talk about hydrogen ions in solution, H +(aq), what you are
actually talking about are hydroxonium ions (H3O+).

According to the Brønsted theory, an acid is a proton donor, and a base is a

proton acceptor.

In an acid-base reaction, each side of the equilibrium has an acid and a base reactant or product, and these
may be neutral species or ions.
H-A + B:(–) A:(–) + B-H
(acid1) (base1) (base2) (acid2)

Structurally related acid-base pairs, such as {H-A and A:(–)} or {B:(–) and B-H} are called conjugate
pairs. Substances that can serve as both acids and bases, such as water, are termed amphoteric.
H-Cl + H2O Cl:(–) + H3O(+)
(acid) (base) (base) (acid)
H3N: + H2O NH4(+) + HO(–)
(base) (acid) (acid) (base)

Example of conjugate pairs

One conjugate pair

HA + H2O H3O+ + A-

the other conjugate pair

When the acid, HA, loses a proton it forms a base, A-. When the base, A-, accepts a proton back again, it
obviously reforms the acid, HA. These two are a conjugate pair.

A second example of conjugate pairs

This is the reaction between ammonia and water that we looked at earlier:

95
 One conjugate pair

NH3(aq) + H2O (l) NH4+(aq) + OH-(aq)

the other conjugate pair

Think first about the forward reaction. Ammonia is a base because it is accepting hydrogen ions from the
water. The ammonium ion is its conjugate acid - it can release that hydrogen ion again to reform the
ammonia.

The water is acting as an acid, and its conjugate base is the hydroxide ion. The hydroxide ion can accept a
hydrogen ion to reform the water.

Looking at it from the other side, the ammonium ion is an acid, and ammonia is its conjugate base. The
hydroxide ion is a base and water is its conjugate acid.

Table 8.1: Some common conjugate acid-base pairs

Acid Base
hydrochloric acid HCl Cl– chloride ion
acetic acid CH3CH2COOH CH3CH2COO– acetate ion
nitric acid HNO3 NO3– nitrate ion
monohydrogen
dihydrogen phosphate ion H2PO4– HPO4–
phosphate ion
hydrogen sulfate ion HSO4– SO42– sulfate ion
hydrogen carbonate
carbonate ion CO32– HCO3–
("bicarbonate") ion
ammonium ion NH4+ NH3 ammonia
iron(III) ("ferric") ion Fe(H2O)63+ Fe(H2O)5OH2+
water H2 O OH– hydroxide ion
hydronium ion H3O+ H2 O water

96
8.3.2 Amphoteric Substances
You may possibly have noticed that in one of the last two examples, water was acting as a base, whereas
in the other one it was acting as an acid. A substance which can act as either an acid or a base is described
as being amphoter.

Water accepts a proton Water loses o proton,

H3O+ H2O OH-
and is acting as a base and is acting as an acid

8.3.3 Comparing the Strengths of Acids

The relative strength of a group of acids (or bases) may be evaluated by measuring the extent of reaction
that each group member undergoes with a common base (or acid). Water serves nicely as the common
base or acid for such determinations. Thus, for an acid H-A, its strength is proportional to the extent of
its reaction with the base water, which is given by the equilibrium constant Keq.

H-A + H2O H3O+ + A:-

Keq 
H O A : 
3
 

HA H 2 O
Since these studies are generally extrapolated to high dilution, the molar concentration of water (55.5) is
constant and may be eliminated from the denominator. The resulting K value is called the acidity
constant, Ka. Clearly, strong acids have larger Ka's than do weaker acids. Because of the very large range
of acid strengths (greater than 1040), a logarithmic scale of acidity (pKa) is normally employed. Stronger
acids have smaller or more negative pKa values than do weaker acids.

Ka 
H O A : 
3
 

HA
 1 
pKa   log Ka  log  
 Ka 

Some useful principles of acid-base reactions are:

Strong acids have weak conjugate bases, and weak acids have strong conjugate bases.
Acid-base equilibria always favor the weakest acid and the weakest base.

Table 8.2: Examples of Brønsted Acid-Base Equilibria

Conjugate Conjugate
Acid-Base Reaction Ka pKa
Acids Bases

HBr + H3 O + + HBr Br–

105 -5
H2 O Br– H3 O + H2 O

H3 O + +
CH3CO2H CH3CO2H CH3CO2– 1.8x10-
4.75
+ H2O H3 O + H2 O 5
CH3CO2–

97
 C2H5OH H3 O + + C2H5OH C2H5O–
10-16 16
+ H2O C2H5O– H3 O + H2 O

NH3 + H3 O + + NH3 NH2–

10-34 34
H2 O NH2- H3 O + H2 O

In all the examples in Table 8.2 water acts as a common base. The last example (NH 3) cannot be
measured directly in water, since the strongest base that can exist in this solvent is hydroxide ion.
Consequently, the value reported here is extrapolated from measurements in much less acidic solvents,
such as acetonitrile.

Since many organic reactions either take place in aqueous environments (living cells), or are quenched or
worked-up in water, it is important to consider how a conjugate acid-base equilibrium mixture changes
with pH. A simple relationship known as the Henderson-Hasselbach equation provides this
information.

Henderson Hasselbach Equation :

pKa  pH  log
HA
A

When the pH of an aqueous solution or mixture is equal to the pKa of an acidic component, the
concentrations of the acid and base conjugate forms must be equal (the log of 1 is 0). If the pH is lowered
by two or more units relative to the pKa, the acid concentration will be greater than 99%. On the other
hand, if the pH (relative to pKa) is raised by two or more units the conjugate base concentration will be
over 99%. Consequently, mixtures of acidic and non-acidic compounds are easily separated by adjusting
the pH of the water component in a two phase solvent extraction.

For example, if a solution of benzoic acid ( pKa = 4.2) in benzyl alcohol ( pKa = 15) is dissolved in ether
and shaken with an excess of 0.1 N sodium hydroxide ( pH = 13), the acid is completely converted to its
water soluble ( ether insoluble ) sodium salt, while the alcohol is unaffected. The ether solution of the
alcohol may then be separated from the water layer, and pure alcohol recovered by distillation of the
volatile ether solvent. The pH of the water solution of sodium benzoate may then be lowered to 1.0 by
addition of hydrochloric acid, at which point pure benzoic acid crystallizes, and may be isolated by
filtration.

8.4 Basicity
The basicity of oxygen, nitrogen, sulfur and phosphorus compounds or ions may be treated in an
analogous fashion. Thus, we may write base-acid equilibria, which define a Kb and a corresponding pKb.
However, a more common procedure is to report the acidities of the conjugate acids of the bases (these
conjugate acids are often "onium" cations). The pKa's reported for bases in this system are proportional to
the base strength of the base.

A useful rule here is: pKa + pKb = 14.

98
We see this relationship in the following two equilibria:
Conjugate Conjugate
Acid-Base Reaction K pK
Acids Bases

NH3 NH4+ Kb =
NH4+ NH3 pKb =
+ + 1.8x10-
H2 O OH– 4.74
H2 O OH– 5

NH4+ H3 O + Ka =
NH4+ NH3 pKa =
+ + 5.5 x
H 3 O+ H2 O 9.25
H2 O NH3 10-10

Table 8.3: Ionization Constants of Inorganic Monoprotic Acids

Common names Formula Acidity Constant pKa

perchloric acid HClO4 ~ 1010 ~ -10
hydrogen iodide HI ~ 109 ~ -9
hydrogen bromide HBr ~ 109 ~ -9
hydrogen chloride HCl ~ 107 ~-7
nitric acid HNO3 ~ 200 ~ -2
thiocyanic acid HSCN 70 -1.85
hydronium ion H3 O + 55 -1.74
chloric acid HClO3 10 -1.0
iodic acid HIO3 0.18 0.75
hypophosphorous acid H2P(O)OH 10-2 2.0
hydrogen fluoride HF 6.6 x 10-4 3.2
nitrous acid HNO2 5.0 x 10-4 3.3
cyanic acid HOCN 3.54 x 10-4 3.45
hydrazoic acid HN3 2.37 x 10-5 4.63
hypochlorous acid HOCl 2.95 x 10-8 7.53
hypobromous acid HOBr 2.3 x 10-9 8.65
hydrocyanic acid HCN 5.8 x 10-10 9.25
ammonium NH4+ 5.8 x 10-10 9.25
hypoiodous acid HOI 10-10 10
hydrogen peroxide H2 O 2 2.5 x 10-12 11.6
water H2 O 1.82 x 10-16 15.74
heavy water D2O 3.5 x 10-17 16.55
ammonia NH3 ca. 10-34 ca. 34

99
Table 8.4: Ionization Constants of Inorganic Polyprotic Acid
Common Name Formula Acidity Constant pKa
H2SO4 K1 = 2.4 x 106 -6.62
sulfuric acid
HSO4-1 K2 = 1.0 x 10-2 1.99
H2CrO4 K1 = 3.55 -0.55
chromic acid
HCrO4-1 K2 = 3.36 x 10-7 6.47
H2SO3 K1 = 1.71 x 10-2 1.77
sulfurous acid
HSO3-1 K2 = 5.98 x 10-8 7.22
H3PO4 K1 = 7.1 x 10-3 2.15
phosphoric acid H2PO4-1 K2 = 6.2 x 10-8 7.21
HPO4-2 K3 = 4.6 x 10-13 12.34
H3PO3 K1 = 1.6 x 10-2 1.8
phosphorous acid
H2PO3-1 K2 = 6.3 x 10-7 6.2
H4P2O7 K1 = 3 x 10-2 1.52
H3P2O7-1 K2 = 4.4 x 10-3 2.36
pyrophosphoric acid
H2P2O7-2 K3 = 2.5 x 10-7 6.60
HP2O7-3 K4 = 5.6 x 10-10 9.25
H2CO3 K1 = 4.35 x 10-7 6.36
carbonic acid
HCO3-1 K2 = 4.69 x 10-11 10.33
H2 S K1 = 9 x 10-8 6.97
hydrogen sulfide
HS-1 K2 = ca.10-15 ca.15
H3BO3 K1 = 7.2 x 10-10 9.14
boric acid H2BO3-1 K2 = 1.8 x 10-13 12.7
HBO3-2 K3 = 1.6 x 10-14 13.8

A common method for evaluating the strength of bases is to report the acidities of the conjugate acids of
the bases (these conjugate acids are often "onium" cations). The resulting pKa's are proportional to the
base strength of the base.

Do you remember the rule which related pKa’s and pKb’s?

? Write it.

Although it is convenient and informative to express pKa values for a common solvent system (usually
water), there are serious limitations for very strong and very weak acids. Thus acids that are stronger than
the hydronium cation, H3O+, and weak acids having conjugate bases stronger than hydroxide anion, OH –,
cannot be measured directly in water solution. Solvents such as acetic acid, acetonitrile and nitromethane
are often used for studying very strong acids. Relative acidity measurements in these solvents may be
extrapolated to water. Likewise, very weakly acidic solvents such as DMSO, acetonitrile, toluene, amines
and ammonia may be used to study the acidities of very weak acids. For both these groups, the
reported pKa values extrapolated to water are approximate, and many have large uncertainties.

An acid is a substance that yields an excess of hydrogen ions when dissolved in water. A
base is a substance that yields an excess of hydroxyl ions when dissolved in water.

100
Lecture 9
Solutions of Acids and Bases

9.1 Introduction
In the previous lecture we defined acid and base in terms of their behavior in water. We also discussed
some theories of acids and bases. In this lecture we will discuss how acid-base chemistry is related to
chemical equilibrium. We will also discuss other concepts related to acids and bases, including pH, acid-
base salts, salt solutions and their properties, and the carbonate system.

Learning Objectives

After studying this lecture you should be able to:

 Explain dissociation of water
 Define various terms related to acid-base solutions
 Explain the concept pH
 Determine pH and pOH of solutions given concentration of H+ and
OH- ions and vice versa
 Use the formula of an acid or base to write the formula of its
conjugate.
 State the fundamental difference between a strong acid and a weak
acid.
 Explain why a hydrogen ion cannot exist in water.
 Describe the leveling effect, and explain its origin.

9.2 Aqueous Solutions of Acids and Bases

9.2.1 Dissociation of Water

All chemical reactions that take place in a single phase (such as in a solution) are theoretically
"incomplete" and are said to be reversible.

101
The ability of acids to react with bases depends on the tendency of hydrogen ions to combine with
hydroxide ions to form water:

H+(aq) + OH–(aq) → H2O (1)

This tendency happens to be very great, so the reaction is practically complete— but not "completely"
complete; a few stray H+ and OH– ions will always be present. What's more, this is true even if you start
with the purest water attainable. This means that in pure water, the reverse reaction, the "dissociation" of
water

H2O → H+(aq) + OH–(aq) (2)

will proceed to a very slight extent. Both reactions take place simultaneously, but (1) is so much faster
than (2) that only a minute fraction of H2O molecules are dissociated.
Liquids that contain ions are able to conduct an electric current. Pure water is practically an insulator, but
careful experiments show that even the most highly purified water exhibits a very slight conductivity that
corresponds to a concentration of both the H+ ion and OH– ions of almost exactly 1.00 × 10–7mol L–1 at
25°C.

Worked Example 9.1

What fraction of water molecules in a litre of water is dissociated?

Answer
1.0 L of water has a mass of 1000 g.
The number of moles in 1000 g of H2O is (1000 g)/(18 g mol–1) = 55.5 mol.
This corresponds to (55.5 mol)(6.02 x 1023 mol-1) = 3.34 x 1025 H2O molecules.
An average of 10-7 mole, or (10-7)(6.02 x 1023) = 6.0 x1016 H2O molecules will be dissociated at any time.
The fraction of dissociated water molecules is therefore:
6.0  1016
 1.8  10 9
3.3  10 25
Thus we can say that only about two out of every billion (10 9) water molecules will be dissociated.

9.2.1.1 Ion Product of Water

The degree of dissociation of water is so small that you might wonder why it is even mentioned here. The
reason stems from an important relationship that governs the concentrations of H+ and OH– ions in
aqueous solutions:
[H+][OH-] = 1.00 x 10-14 (3)

The quantity 1.00 x 10–14 is commonly denoted by Kw. Its value varies slightly with temperature, pressure,
and the presence of other ions in the solution.
The square brackets [ ] refer to the concentrations (in moles per litre) of the substances they enclose.

This expression is known as the ion product of water, and it applies to all aqueous solutions, not just to
pure water. The consequences of this are far-reaching, because it implies that if the concentration of H + is
large, that of OH– will be small, and vice versa. This means that H+ ions are present in all aqueous
solutions, not just acidic ones.

102
This leads to the following important definitions, which you must know:

Acidic solution [H+] > [OH-]

Alkaline (“basic”) solution [H+] < [OH-]
Neutral solutions [H+] = [OH-] = 1.00 x 10-7 mol L-1
Take special note of the following definition:
A neutral solution is one in which the concentrations of H+ and OH- ions are identical.

The values of these concentrations are constrained by Eq. 3. Thus, in a neutral solution,
both the hydrogen- and hydroxide ion concentrations are 1.00 × 10 –7 mol L–1
[H+][OH–] = [1.00 × 10–7][1.00 × 10–7] =1.00 × 10–14
Hydrochloric acid is a typical strong acid that is totally dissociated in solution
HCl  H3O+(aq) + Cl-(aq)

A 1.0M solution of HCl in water therefore does not really contain any significant concentration of HCl
molecules at all; it is a solution in of H3O+and Cl– in which the concentrations of both ions are 1.0 mol L–
1. The concentration of hydroxide ion in such a solution, according to Eq 2, is:

OH  

Kw
 
H

1.00  10 14
1 mol L1
 1.00  10 14 mol L1

Similarly, the concentration of hydrogen ion in a solution made by dissolving 1.0 mol of sodium
hydroxide in water will be 1.00 x 10–14 mol L–1

9.3 pH
When dealing with a range of values (such as the variety of hydrogen ion concentrations encountered in
chemistry) that spans many powers of ten, it is convenient to represent them on a more compressed
logarithimic scale. By convention, we use the pH scale to denote hydrogen ion concentrations:

pH = - log [H+] (4)

or conversely,
[H+] = 10-pH

This notation was devised by the Danish chemist Søren Sørensen (1868-1939) in 1909. There are several
accounts of why he chose "pH"; a likely one is that the letters stand for the French term pouvoir hydrogène,
meaning "power of hydrogen"— "power" in the sense of an exponent. It has since become common to
represent other small quantities in "p-notation". For this course you need to know the following:

pOH = – log10 [OH–]

pKw = – log Kw (= 14 when Kw = 1.00 × 10–14)

103
Note that pH and pOH are expressed as numbers without any unit, since logarithms must be
dimensionless. Recall from equation (3) that [H +][OH-] = 1.00 x 10-14; if we write this in “p-notation” it
becomes

pH + pOH = 14 (5)
In a neutral solution at 25°C, pH = pOH = 7.0

As pH increases, pOH diminishes; a higher pH corresponds to an alkaline solution, a lower pH to an

acidic solution. In a solution with [H+] = 1 M , the pH would be 0; in a 0.00010 M solution of H+, it
would be 4.0. Similarly, a 0.00010 M solution of NaOH would have a pOH of 4.0, and thus a pH of 10.0.
It is very important that you thoroughly understand the pH scale, and be able to convert between [H +] or
[OH–] and pH in both directions.

Worked example 9.2

The pH of blood must be held very close to 7.40. Find the hydroxide ion concentration that corresponds
to this pH.
Answer
The pOH will be (14.0 – 7.40) = 6.60.
[OH–] = 10–pOH = 10–6.6 = 2.51 x 10–7 M

(a)

104
 (b)
Figure 9.1(a,b): The range of pH values runs from about 0 to 14

Figure 9.1(a, b) will help give you a general feeling for where common substances fall on the pH scale.
Notice especially that:

 most foods are slightly acidic;

 The principal "bodily fluids" are slightly alkaline, as is seawater— not surprising, since early
animal life began in the oceans.

 The pH of freshly-distilled water will drift downward as it takes up carbon dioxide from the air;
CO2 reacts with water to produce carbonic acid, H2CO3.

 The pH of water that occurs in nature varies over a wide range. Groundwaters often pick up
additional CO2 respired by organisms in the soil, but can also become alkaline if they are in
contact with carbonate-containing sediments. "Acid" rain is by definition more acidic than pure
water in equilibrium with atmospheric CO2, owing mainly to sulfuric and nitric acids that
originate from fossil-fuel emissions of nitrogen oxides and SO2.

The word "about" in the above statement reflects the fact that at very high concentrations (10 M
hydrochloric acid or sodium hydroxide, for example,) a significant fraction of the ions will be associated
into neutral pairs such as H+·Cl–, thus reducing the concentration of “available” ions to a smaller value
which we will call the effective concentration. It is the effective concentration of H+ and OH– that determines the
pH and pOH. For solutions in which ion concentrations don't exceed 0.1 M, the formulas pH = –
log [H+] and pOH = –log[OH–] are generally reliable, but don't expect a 10.0 M solution of a strong acid
to have a pH of exactly –1.00!

Worked example 9.3

Find the pH of a 0.20 M solution of sodium propionate (C 2H5COONa), where the Ka of propionic acid
= 1.34 x 10-5. (Hint: Kw = KaKb)

Answer
We need to get the Kb of the propionate ion first:

105
 1.00  10 14
Kb   7.46  10 10
1.34  10 5

7.46  10 10 
x x 
0.20  x
x = √[(7.46 x 10 ) (0.20)]
-10

x = 1.22 x 10-5 M = [OH-]

pOH = - log 1.22 x 10-5 = 4.91
pH = 14 - 4.91 = 9.09

Worked example 9.4

Determine the Ka of the weak acid HX knowing that a 0.10 M solution of LiX has pH = 8.90. (Hint: you
have to work backwards from the example calculations.)

Answer
The key is to see that the Kb of X- is related to the Ka of HX (what we want to get) by way of Kw.
This is the reaction of interest:

X- + H2O  HX + OH-

We need to fill in the right side of the Kb expression for X-. The pH is where we start:
Since pH = 8.90, the pOH = 14 - 8.90 = 5.10
We get the pOH because it will give us the two values in the numerator of the K b expression for X-

[OH-] = 10-pOH = 10-5.10 = 7.9 x 10-6 M

Now, we can write the Kb expression. Remember that [X-] = [OH-]:


7.9  10 7.9  10 
6 6
 6.2  10 10
0.10  7.9  10 
Kb 6

9.3.1 pH Indicators
The colours of many dye-like compounds depend on the pH, and serve as useful indicators to determine
whether the pH of a solution is above or below a certain value.

Proton donors and acceptors

The older Arrhenius theory of acids and bases viewed them as substances which produce hydrogen ions
or hydroxide ions on dissociation. As useful a concept as this has been, it was unable to explain why NH 3,
which contains no OH– ions, is a base and not an acid, why a solution of FeCl3 is acidic, or why a solution
of Na2S is alkaline.

A more general theory of acids and bases was developed by Franklin in 1905, who suggested that the
solvent plays a central role. According to this view, an acid is a solute that gives rise to a cation (positive ion)
characteristic of the solvent, and a base is a solute that yields a anion (negative ion) which is also
characteristic of the solvent. The most important of these solvents is of course H 2O, but Franklin's
insight extended the realm of acid-base chemistry into non-aqueous systems as we shall see in a later
lesson.

106
9.4 Bronstead Acids and Bases

In 1923 the Danish chemist J.N. Brønsted, building on Franklin's theory, proposed that

An acid is a proton donor; a base is a proton acceptor.

In the same year the English chemist T.M. Lowry published a paper setting forth some similar ideas
without producing a definition; in a later paper Lowry himself points out that Brønsted deserves the
major credit, but the concept is still widely known as the Brønsted-Lowry theory. These definitions carry
a very important implication:

Note: a substance cannot act as an acid without the presence of a base to accept
the proton, and vice versa.

As a very simple example, consider the equation that Arrhenius wrote to describe the behavior of
hydrochloric acid:
HCl  H+ + A-

This is fine as it goes, chemists still write such an equation as a shortcut. But in order to represent this
more realistically as a proton donor-acceptor reaction, we now depict the behaviour of HCl in water by:

HCl + H2O Cl- + H3O+

acid base hydronium
ion
In which the acid HCl donates its proton to the acceptor (base) H 2O

How can you explain the reaction of ammonia with water to produce the alkaline
? solution?

You understand that there are no OH- ions in ammonia but we get an alkaline solution which indicates
that there are excess OH-ions. These OH-ions must have been produced as follows:
NH3 + H2O NH4+ + OH-
base acid

NH3 is not an Arrhenius base. It is, however, a Brønsted base. In this case, the water molecule acts as the
acid, donating a proton to the base NH3 to create the ammonium ion NH4+.
The foregoing examples illustrate several important aspects of the Brønsted-Lowry concept of acids and
bases:

 A substance cannot act as an acid unless a proton acceptor (base) is present to

receive the proton;

 A substance cannot act as a base unless a proton donor (acid) is present to supply

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 the proton;

 Water plays a dual role in many acid-base reactions; H2O can act as a proton
acceptor (base) for an acid, or it can serve as a proton donor (acid) for a base (as we
saw for ammonia).

 The hydronium ion H3O+ plays a central role in the acid-base chemistry of aqueous
solutions.

9.5 The Hydronium Ion (H3O+)

Hydrogen ions cannot exist in water

There is another serious problem with the Arrhenius view of an acid as a substance that dissociates in
water to produce a hydrogen ion. The hydrogen ion is no more than a proton, a bare nucleus. Although it
carries only a single unit of positive charge, this charge is concentrated into a volume of space that is only
about a hundred-millionth as large as the volume occupied by the smallest atom. The resulting
extraordinarily high charge density of the proton strongly attracts it to any part of a nearby atom or molecule
in which there is an exess of negative charge. In the case of water, this will be the lone pair (unshared)
electrons of the oxygen atom; the tiny proton will be buried within the lone pair and will form a shared-
electron (coordinate) bond with it, creating a hydronium ion, H3O+. In a sense, H2O is acting as a base
here, and the product H3O+ is the conjugate acid of water:
H H +
H
+ O O

H H

H+ ion water Hydronium ion

Owing to the overwhelming excess of H2O molecules in aqueous solutions, a bare hydrogen ion has no
chance of surviving in water. Although other kinds of dissolved ions have water molecules bound to them
more or less tightly, the interaction between H+ and H2O is so strong that writing “H+(aq)” hardly does it
justice, although it is formally correct. The formula H 3O+ more adequately conveys the sense that it is
both a molecule in its own right, and is also the conjugate acid of water.

Interestingly, experiments indicate that the proton does not stick to a single H 2O molecule, but changes
partners many times per second. This molecular promiscuity, a consequence of the uniquely small size
and mass the proton, allows it to move through the solution by rapidly hopping from one H 2O molecule
to the next, creating a new H3O+ ion as it goes. The overall effect is the same as if the H 3O+ ion itself
were moving. Similarly, a hydroxide (OH-) ion, which can be considered to be a “proton hole” in the
water, serves as a landing point for a proton from another H 2O molecule, so that the OH– ion hops about
in the same way.

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9.6 Strong Acids and Weak Acids

We look upon the generalized acid-base reaction

HA + H2O H3O+ + A-
acid base Conjugate Conjugate
acid base

as a competition of two bases for a proton:

9.6.1 Definition of a "Strong" Acid

If the base H2O overwhelmingly wins this tug-of-war, then the acid HA is said to be a strong acid. This
is what happens with hydrochloric acid and the other common strong "mineral acids" H2SO4, HNO3, and
HClO4:

hydrochloric acid HCl + H2O → Cl– + H3O+

sulfuric acid H2SO4 + H2O → HSO4– + H3O+
nitric acid HNO3 + H2O → NO3– + H3O+
perchloric acid HClO4 + H2O → ClO4– + H3O+

Solutions of these acids in water are really solutions of the ionic species shown in heavy type on the right.
This being the case, it follows that what we call a 1 M solution of "hydrochloric acid" in water, for
example, does not really contain a significant concentration of HCl at all; the only real a acid present in
such a solution is H3O+!

These considerations give rise to two important rules:

 H3O+ is the strongest acid that can exist in water

 All strong acids appear to be equally strong in water

9.6.2 Salts of Weak Acids give Alkaline Solutions

The fact that HCN is a weak acid implies that the cyanide ion CN– reacts readily with protons, and is thus
is a relatively good base. As evidence of this, a salt such as KCN, when dissolved in water, yields a slightly
alkaline solution:
CN– + H2O → HCN + OH–

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This reaction is still sometimes referred to by its old name hydrolysis ("water splitting"), which is literally
correct but tends to obscure its identity as just another acid-base reaction. Reactions of this type take
place only to a small extent; a 0.1M solution of KCN is still, for all practical purposes, 0.1M in cyanide
ion.
In general, the weaker the acid, the more alkaline will be a solution of its salt. However, it would be going
to far to say that "ordinary weak acids have strong conjugate bases." The only really strong base is
hydroxide ion, OH–, so the above statement would be true only for the very weak acid H2O.

9.6.3 Strong Bases and Weak Bases

The only really strong bases you are likely to encounter in day-to-day chemistry are alkali-metal
hydroxides such as NaOH and KOH, which are essentially solutions of the hydroxide ion. Most other
compounds containing hydroxide ions such as Fe(OH)3 and Ca(OH)2 are not sufficiently soluble in water
to give highly alkaline solutions, so they are not usually thought of as strong bases. There are actually a
number of bases that are stronger than the hydroxide ion — best known are the oxide ion O2– and the
amide ion NH2–, but these are so strong that they can rob water of a proton:
O2– + H2O → 2 OH–
NH2– + H2O → NH3 + OH–

Hydroxide ion is the strongest base that can exist in aqueous solution.

9.6.4 Salts of Weak Bases give Acidic Solutions

The most common example of this is ammonium chloride, NH4Cl, whose aqueous solutions are distinctly
acidic:
NH4+ + H2O → NH3 + H3O+
Because this (and similar) reactions take place only to a small extent, a solution of ammonium chloride
will only be slightly acidic.

9.6.5 Autoprotolysis
From some of the examples given above, we see that water can act as an acid
CN– + H2O → HCN + OH–
and as a base
NH4+ + H2O → NH3 + H3O+
If this is so, then there is no reason "why water-the-acid" cannot donate a proton to "water-the-base":

This reaction is known as the autoprotolysis of water.

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Chemists still often refer to this reaction as the "dissociation" of water and use the Arrhenius-style
equation H2O → H+ + OH– as a kind of shorthand.

This process occurs to only a tiny extent. It does mean, however, that hydronium and hydroxide ions are
present in any aqueous solution.

? Can other liquids exhibit autoprotolysis?

The answer is yes. The most well-known example is liquid ammonia:

2 NH3 → NH4+ + NH2–
Even pure liquid sulfuric acid can play the game:
2 H2SO4→ H3SO4+ + HSO4–
Each of these solvents can be the basis of its own acid-base "system", parallel to the familiar "water
system".

9.6.6 Ampholytes
Water, which can act as either an acid or a base, is said to be amphiprotic: it can "swing both ways". A
substance such as water that is amphiprotic is called an ampholyte.

It is of course the amphiprotic nature of water that allows it to play its special role in ordinary aquatic
acid-base chemistry. But many other amphiprotic substances can also exist in aqueous solutions. Any
such substance will always have a conjugate acid and a conjugate base, so if you can recognize these two
conjugates of a substance, you will know it is amphiprotic.

9.7 The Carbonate System

For example, the triplet set {carbonic acid, bicarbonate ion, carbonate ion} constitutes an amphiprotric
series in which the bicarbonate ion is the ampholyte, differing from either of its neighbours by the
addition or removal of one proton:

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If the bicarbonate ion is both an acid and a base, it should be able to exchange a proton with itself in an
autoprotolysis reaction:

HCO3– + HCO3– → H2CO3 + CO32–

Your very life depends on the above reaction! CO2, a metabolic by-product of every cell in your body,
reacts with water to form carbonic acid H2CO3 which, if it were allowed to accumulate, would make your
blood fatally acidic. However, the blood also contains carbonate ion, with reacts according to the reverse
of the above equation to produce bicarbonate which can be safely carried by the blood to the lungs. At
this location the autoprotolysis reaction runs in the forward direction, producing H2CO3 which loses
water to form CO2 which gets expelled in the breath. The carbonate ion is recycled back into the blood to
eventually pick up another CO2 molecule.

If you can write an autoprotolysis reaction for a substance, then that substance is amphiprotic.

Summary
The Bronsted–Lowry theory describes an acid as a proton donor and a base as a proton accepter. Every
acid has a conjugate base and vice versa. In an acid–base reaction a proton is transferred from the acid to
a base. In general acid–base reactions are reversible, but equilibrium is displaced in the direction from the
stronger acids and bases to their weaker conjugates.

In pure water and aqueous solutions, self-ionization occurs to a very slight extent, producing H3O+ and
OH-, as described by the equilibrium constant Kw. The designations pH and pOH are often used to
describe the concentrations of H3O+ and OH- in aqueous solutions.
Strong acids ionize completely in aqueous solutions to produce H3O+, and bases dissociate completely to
produce OH-. In aqueous solutions, the following are described as strong acids: HClO 4, HI, HBr, HCl,
HNO3and H2SO4 (first stage ionization). With weak acids and bases ionization is reversible and must be
described through the ionization constants, Ka and Kb.

Exercise
1. Calculate [H+] ion in water solutions where [OH-] ion is:
(a) 1.00 × 10-4 M
(b) 5.00 × 10-7 M
2. Calculate pH and pOH in solutions where [H+] is
(a) 5.0 × 10-9 M
(b) 6.1 × 10-12 M
3. Calculate the pH of a solution made by dissolving 0.20 grams of HNO 3 in water and diluting to a
total volume of 500.0 mL.

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4. Why do aluminium and chromium precipitate as hydroxides rather than as sulfides?
5. Explain why ammonium carbonate rather than sodium carbonate is used in the precipitation of
group IV cations?
6. Why must ammonium ions be removed before making the chemical test for the potassium ions?
7. When MgNH3PO4 is heated to a high temperature (1000°C) it is converted to magnesium
diphosphate, Mg2P2O7. Write a balanced equation for this reaction.
8. In a group I analysis, a student obtained a precipitate containing both AgCl and PbCl 2. Suggest
one reagent that would allow her to separate AgCl(s) from PbCl 2(s).
9. At pH = 1.00, will the compound MS precipitate from a solution saturated with H 2S (0.10) if
[M2+] = 0.20 M initially? (Ksp for MS = 6.0 × 10-20).
10. Describe a simple test that would allow you to distinguish between AgNO 3(s) and Cu (NO3)2(s).
11. Suggest a reagent that would allow you to separate Al3+ from Fe3+.

References
1. Petrucci, R. H., Harwood, W. S., Herring, G.E. and Madura, J. (2006) General Chemistry:
Principles and Modern Application, 9th Edition. Prentice Hall.
2. Chang, R. (2003). General Chemistry: The Essential Concepts. 3rd Ed. The McGrow-Hill
Companies, Inc., New York.
3. Burns, R.A. (2002) Fundamentals of Chemistry 4 th Edition. Prentice Hall.
4. Svehla, G.; Vogel’s Qualitative Inorganic Analysis, Orient Longman, 6th Ed., 1987

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Lecture 10
Alkanes

10.1 Introduction
Hydrocrabons are compounds containing carbon and hydrogen only. These include alkanes, cycloalkanes,
alkenes and alkynes. The Section deals with their nomenclature, isomerism, physical properties, and
chemical reactivity.

This Lecture introduces you to the first group of Hydrocarbons, the Alkanes. You will discuss the general
formula of alkanes and their nomenclature using the IUPAC naming system; their physical properties and
reactivity.

Learning Objectives

At the end of this Lecture you should be able to

 Write the general formula of alkanes
 Write names and formulas of different alkanes using the IUPAC system.
 Describe the physical and chemical properties of alkanes
 Write equations for different reactions of alkanes, including combustion
and halogenations
 Describe general methods of preparation of alkanes

10.2 Definition of Alkanes

Alkanes are the simplest family of hydrocarbons - compounds containing carbon and hydrogen only.
They only contain carbon-hydrogen bonds and carbon-carbon single bonds. Alkanes are also known as
‘saturated hydrocarbons’.
Alkanes can be:
- Straight chain
- Branched
- Cyclic

Table 10.1 lists the first six alkanes:

Table 10.1: Alkanes
Name Formula Name Formula
Methane CH4 Butane C4H10
Ethane C2H6 Pentane C5H12
Propane C3H8 Hexane C6H14

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 Table 10.2

Note that: All of them conform with the the general formula of CnH2n+2

10.3 Nomenclature of Alkanes

The International Union of Pure and Applied Chemistry (IUPAC) has formulated general rules for
nomenclature of organic compounds. Systematic names of compounds is based on four essential
elements:

 the main part of the molecule with the number of carbon atoms

 the location and identity of various substituent groups in the molecule

 the primary functional group

 the location of the primary functional group

The following are the IUPAC rules for naming alkanes.

1. Find the parent hydrocarbon, which is the longest continuous carbon chain. Use this as the
parent name of the molecule, ending with ‘-ane’. Look at the following example:

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Note that A has 9 carbon atoms in the longest continuous chain with a substituent on carbon
numbers 3 and 6, while B has 8 carbon atoms in the longest chain. Therefore, alkane A has the parent
name of “nonane”.
Notice that both the structures are same but if you choose to take the wrong lane while counting the
carbon atoms from one end to another, you can end up naming the structure with a wrong name.

2. Number the chain consecutively, starting at the end nearest a substituent group.
Start numbering from the end where you first meet a substituent.

3. Identify the location of each substituent group by an appropriate number and name.

Note that in the above example, there is a methyl group in C2, an ethyl group in C3 and a methyl
group in C7.

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 4. Assembling the full name
List all substituents in alphabetical order. If there are two or more similar substituents use -di, -
tri, -tetra to denote them.

Examples

Exercise 10.2
Draw structures of the following compounds
3-ethyl-4-methylheptane
(ii) 2,3-diethyl-3-methylheptane
(iii) 2,2,4,6-tetramethyl-5-propyldecane
Do you think the above names are correct according to the IUPAC system? If not, what
are the correct names of the drawn structures.
Name the following compound:

10.3.1 Isomerism
All the alkanes with 4 or more carbon atoms in them show structural isomerism. This means that there
are two or more different structural formula that you can draw for each molecular formula.

For example, C4H10 could be either of these two different molecules:

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 Figure 10.1: Structural isomers of butane

These are called respectively butane and 2-methylpropane.

10.4 Physical Properties of Alkanes

10.4.1 Boiling points

Figure 10.2: Boiling Points of the Alkanes

The boiling points shown are all for the "straight chain" isomers where there are more than one. Notice
that the first four alkanes are gases at room temperature. Solids don't start to appear until about C 17H36.
You can't be more precise than that because each isomer has a different melting and boiling point. By the
time you get 17 carbons into an alkane, there are unbelievable numbers of isomers!

10.4.2 Solubility
Alkanes are virtually insoluble in water, but dissolve in organic solvents. The liquid alkanes are good
solvents for many other covalent compounds.

10.5 Reactions of Alkanes

Alkanes contain strong carbon-carbon single bonds and strong carbon-hydrogen bonds. The carbon-
hydrogen bonds are only very slightly polar and so there aren't any bits of the molecules which carry any
significant amount of positive or negative charge which other things might be attracted to.
The net effect is that alkanes have a fairly restricted set of reactions.

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You can
 burn them - destroying the whole molecule;
 react them with some of the halogens, breaking carbon-hydrogen bonds;
 crack them, breaking carbon-carbon bonds.

10.5.1 Combustion of Alkanes to form carbon dioxide and water

Complete combustion (in the presence of sufficient oxygen) of any hydrocarbon produces carbon dioxide
and water. It is quite important that you can write properly balanced equations for these reactions.
Examples:
1. Combustion of propane

2. Combustion of butane

Or

10.5.2 Reaction of Alkanes with Halogens

Alkanes undergo a substitution reaction with halogens in the presence of light. For instance, in ultraviolet
light, methane reacts with halogen molecules such as chlorine and bromine. This reaction is a substitution
reaction because one of the hydrogen atoms from the methane is replaced by a bromine atom.
CH4 + Br2 → CH3Br + HBr

10.5.3 Cracking of Alkanes

Cracking is the process whereby complex organic molecules or long chain hydrocarbons are broken down
into simpler molecules such as light hydrocarbons, by the breaking of carbon-carbon bonds.

There are two types of cracking

(i) Thermal cracking – Using high temperature (450°C to 750°C) and pressure without a catalyst
(up to about 70 atmospheres).
(ii) Catalytic cracking – Using catalyst at low temperature and pressure.

The source of the large hydrocarbon molecules is often the naphtha fraction or the gas oil fraction
from the fractional distillation of crude oil (petroleum). These fractions are obtained from the
distillation process as liquids, but are re-vaporised before cracking. There isn't any single unique
reaction happening in the cracker. The hydrocarbon molecules are broken up in a fairly random way

119
 to produce mixtures of smaller hydrocarbons, some of which have carbon-carbon double bonds. One
possible reaction involving the hydrocarbon C15H32 might be:

Or, showing more clearly what happens to the various atoms and bonds:

This is only one way in which this particular molecule might break up. The ethene and propene are
important materials for making plastics or producing other organic chemicals. The octane is one of the
molecules found in petrol (gasoline).

10.6 General Methods of Preparation of Alkanes

1. Hydrogenation of Alkenes
Alkanes can be obtained from the addition of hydrogen to alkenes known as a “hydrogenation” or
“reduction”. In this reaction a molecule of hydrogen is added to the alkene molecule at the site of
unsaturation i.e. where the double bond is. This is achieved under mild conditions when a catalyst is used
to bring about this change.

2. Hydrogenation (reduction) of Haloalkanes

Haloalkanes can give the alkanes if they are exposed to an environment where hydrogen atoms are
generated. The hydrogen atom replaces the halogen atom from the haloalkane.

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3. Reduction of alcohols by very strong reducing agents
A very strong reducing agent will remove the -OH group from alcohol, replacing it with an H atom.

4. Reduction of carbonyl compounds (aldehydes and ketones)

Using the same conditions of very strong reducing agent, carbonyl compounds can be reduced to alkanes
by removing the = O group and adding 2H atoms.

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Lecture 11
Cycloalkanes

11.1 Introduction

Learning Objectives

At the end of this Module you should be able to:

 Write the general formula of cycloalkanes
 Write names of different cycloalkanes.
 Describe the physical properties and chemical reactivity of cycloalkanes
 Write equations for different reactions of cycloalkanes

11.2 Definition of Cycloalkanes

Cycloalkanes, also known as cyclic alkanes only contain carbon-hydrogen bonds and carbon-carbon single
bonds, but this time the carbon atoms are joined up in a ring. The smallest cycloalkane is cyclopropane.

Figure 11.1: The first four cycloalkanes

If you count the carbons and hydrogens, you will see that they no longer fit the general formula C nH2n+2.
By joining the carbon atoms in a ring, you have had to lose two hydrogen atoms. You are unlikely to ever
need it, but the general formula for a cycloalkane is CnH2n.

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 The general formula for a cycloalkane is CnH2n. Thus the general formula for
cycloalkanes is the same as that of straight chain alkenes

Don't imagine that these are all flat molecules. All the cycloalkanes from cyclopentane upwards exist as
"puckered rings". Cyclohexane, for example, has a ring structure which looks like this:

Figure11.2: the chair structure cyclopentane

This is known as the "chair" form of cyclohexane - from its shape which vaguely resembles a chair.

Table 11.1 Examples of simple Cycloalkanes

Examples of Simple Cycloalkanes

Name Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane Cycloalkane

Molecular
C 3 H6 C 4 H8 C5H10 C6H12 C7H14 CnH2n
Formula

Structural
(CH2)n
Formula

Line
Formula

Substituted cycloalkanes are named in a fashion very similar to that used for naming branched alkanes.

11.3 Phyisical Properties of Cycloalakanes

11.3.1 Solubility
Cycloalkanes have boiling points which are about 10 - 20 K higher than the
corresponding straight chain alkane.

Explanations
There isn't much electronegativity difference between carbon and hydrogen, so there is hardly any bond
polarity. The molecules themselves also have very little polarity. A totally symmetrical molecule like
methane is completely non-polar.

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11.3.2 Solubility
The facts: With the electron pairs this close together, there is a lot of repulsion between the bonding pairs
joining the carbon atoms. That makes the bonds easier to break.
What follows applies equally to alkanes and cycloalkanes
Alkanes are virtually insoluble in water, but dissolve in organic solvents. The liquid alkanes are good
solvents for many other covalent compounds.

i. Solubility in water
When a molecular substance dissolves in water, you have to:

 Break the intermolecular forces within the substance. In the case of the alkanes, these are Van
der Waals dispersion forces.

 Break the intermolecular forces in the water so that the substance can fit between the water
molecules. In water the main intermolecular attractions are hydrogen bonds
Breaking either of these attractions costs energy, although the amount of energy to break the Van der
Waals dispersion forces in something like methane is pretty negligible. That isn't true of the hydrogen
bonds in water, though.
As something of a simplification, a substance will dissolve if there is enough energy released when new
bonds are made between the substance and the water to make up for what is used in breaking the original
attractions. The only new attractions between the alkane and water molecules are Van der Waals. These
don't release anything like enough energy to compensate for what you need to break the hydrogen bonds
in water. The alkane doesn't dissolve.

ii Solubility in organic solvents

In most organic solvents, the main forces of attraction between the solvent molecules are Van der Waals -
either dispersion forces or dipole-dipole attractions. That means that when an alkane dissolves in an
organic solvent, you are breaking Van der Waals forces and replacing them by new Van der Waals forces.
The two processes more or less cancel each other energetically - so there isn't any barrier to solubility.

11.4 Chemical Reactivity of Cycloalakanes

Cycloalkanes are very similar to the alkanes in reactivity, except for the very small ones - especially
cyclopropane. Cyclopropane is much more reactive than you would expect. In the presence of UV light,
cyclopropane will undergo substitution reactions with chlorine or bromine just like a non-cyclic alkane.
The reason has to do with the bond angles in the ring. Normally, when carbon forms four single bonds,
the bond angles are about 109.5°. In cyclopropane, they are 60°.

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With the electron pairs this close together, there is a lot of repulsion between the bonding pairs joining
the carbon atoms. That makes the bonds easier to break. This means that the only attractions between
one molecule and its neighbours will be Van der Waals dispersion forces. These will be very small for a
molecule like methane, but will increase as the molecules get bigger. That's why the boiling points of the
alkanes increase with molecular size.

Where you have isomers, the more branched the chain, the lower the boiling point tends to be. Van der
Waals dispersion forces are smaller for shorter molecules, and only operate over very short distances
between one molecule and its neighbours. It is more difficult for short fat molecules (with lots of
branching) to lie as close together as long thin ones. For example, the boiling points of the three isomers
of C5H12 are:

Table 11.2: Boiling points of the three isomers of pentane

Compound Boiling Point (K)
Pentane 309.2
2-methylbutane 301.0
2,2-dimethylpropane 282.6

The slightly higher boiling points for the cycloalkanes are presumably because the molecules can get
closer together because the ring structure makes them tidier and less "wriggly"!

11.4.1 Halogenation of Cycloalkanes

Cycloalkanes react with the halogens (fluorine, chlorine, bromine and iodine) - mainly concentrating on
chlorine and bromine.
For example, chlorination of cyclohexane to form chlorocyclohexane:

11.4.2 Combustion of Cyclohexanes

Just like any other hydrocarbon, complete combustion (given sufficient oxygen) of cycloalkanes produce
carbon dioxide and water.

Note that the hydrocarbons become harder to burn as the molecules get bigger. This is because the
bigger molecules don't vaporise so easily - the reaction is much better if the oxygen and the hydrocarbon
are well mixed as gases. If the liquid isn't very volatile, only those molecules on the surface can react with
the oxygen.

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Lecture 12
Alkenes

12.1 Introduction
This Lecture introduces you to another group of Hydrocarbons, the Alkenes. You will discuss the general
formula of alkenes and their nomenclature using the IUPAC naming system; their physical properties and
reactions.

Learning Objectives
At the end of this Module you should be able to

 Write the general formula of Alkenes

 Write names and formulas of different alkenes using the IUPAC
system.
 Describe the physical and chemical properties of Alkenes
 Write equations for different reactions of Alkenes.
 State and apply the Markovnikov’s Rule for addition of Hydrogen
halides to unsymmetrical Alkenes
 Describe general methods of preparation of Alkenes.

12.2 Definition of Alkenes

? What are alkenes?

Alkenes are a family of hydrocarbons containing a carbon-carbon double bond (C=C). The first two are:

Table 12.1: The first few Alkenes

Name Formula Name Formula
Ethene C2H4 Pentene C5H10
Propene C3H6 Hexene C6H12
Butene C4H8 Heptene C7H14

You will note that their general formula is CnH2n

After the first two alkenes there are isomers which affect the names.

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12.2.1 Isomerism in the Alkenes

(i) Structural isomerism

All the alkenes with 4 or more carbon atoms in them show structural isomerism. This means that there are
two or more different structural formulae that you can draw for each molecular formula.
For example, with C4H8, it isn't too difficult to come up with these three structural isomers:

Figure 12.1: Structural isomers of butene

There is, however, another isomer. But-2-ene also exhibits geometric isomerism.

(ii) Geometric (cis-trans) isomerism

The carbon-carbon double bond doesn't allow any rotation about it. That means that it is possible to have
the CH3 groups on either end of the molecule locked either on one side of the molecule or opposite each
other.
These are called cis-but-2-ene (where the groups are on the same side) or trans-but-2-ene (where they are
on opposite sides).

Figure 12.2: Geometrical isomerism of but-2-ene

12.3 Nomenclature of Alkenes

The IUPAC Rules are applied for naming alkene. The ending –ene indicates an alkene. The longest chain
chosen for the root name must include both carbon atoms of the double bond. The root chain must be
numbered from the end nearest a double bond carbon atom.

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 1. Name the parent hydrocarbon by locating the longest carbon chain that contains the double
bond and name it according to the number of carbons with the suffix –ene.

2. (a) Number the carbons of the parent chain so the double bond carbons have the lowest possible
numbers.
H3C-CH2-CH2-CH=CH-CH3 This is 2-hexene
6 5 4 3 2 1

(b) If the double bond is equidistant from each end, number so the first substituent has the
lowest number.

3. If there are subtituents (branches), write out the full name, numbering the substituents according
to their positions in the chain and list them in alphabetical order.

4. Note that alkenes may have more than one double bond. The parent name will end with a suffix
that indicates the number of C=C double bond in the compound (-end for one C=C; diene for
two C=C; -triene for three C=C)

12.4 Properties of Alkenes

12.4.1 Physical Properties of the Alkenes

(i) Boiling Points

The boiling point of each alkene is very similar to that of the alkane with the same number of carbon
atoms. Ethene, propene and the various butenes are gases at room temperature. All the rest that you are
likely to come across are liquids.
In each case, the alkene has a boiling point which is a small number of degrees lower than the
corresponding alkane. The only attractions involved are Van der Waals dispersion forces, and these
depend on the shape of the molecule and the number of electrons it contains. Each alkene has 2 fewer
electrons than the alkane with the same number of carbons.

(ii) Solubility
Alkenes are virtually insoluble in water, but dissolve in organic solvents.

12.4.2 Chemical Reactivity

(i) Bonding in the alkenes
We just need to look at ethene, because what is true of C=C in ethene will be equally true of C=C in
more complicated alkenes.
Ethene is often modeled like this:

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The double bond between the carbon atoms is, of course, two pairs of shared electrons. What the
diagram doesn't show is that the two pairs aren't the same as each other.

One of the pairs of electrons is held on the line between the two carbon nuclei as you would expect, but
the other is held in a molecular orbital above and below the plane of the molecule. A molecular orbital is
a region of space within the molecule where there is a high probability of finding a particular pair of
electrons.

In this diagram, the line between the two carbon atoms represents a normal bond - the pair of shared
electrons lies in a molecular orbital on the line between the two nuclei where you would expect them to
be. This sort of bond is called a sigma () bond.

The other pair of electrons is found somewhere in the shaded part above and below the plane of the
molecule. This bond is called a pi () bond. The electrons in the pi bond are free to move around anywhere
in this shaded region and can move freely from one half to the other.

The pi electrons are not as fully under the control of the carbon nuclei as the electrons in the sigma bond
and, because they lie exposed above and below the rest of the molecule, they are relatively open to attack
by other things.

12.5 Reactions of Alkenes

The important reactions all centre around the double bond. Typically, the pi bond breaks and the
electrons from it are used to join the two carbon atoms to other things. Alkenes undergo addition reactions.
For example, using a general molecule X-Y:

The rather exposed electrons in the pi bond are particularly open to attack by things which carry some
degree of positive charge. These are called electrophiles. If you explore the rest of the alkene menu, you
will find lots of examples of this kind.

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12.5.1 The Combustion of Alkenes

Like any other hydrocarbons, alkenes burn in air or oxygen, but these reactions are unimportant. Alkenes
are too valuable to waste in this way.

Complete Combustion
Complete combustion (given sufficient oxygen) of any hydrocarbon produces carbon dioxide and water.

Equations
It is quite important that you can write properly balanced equations for these reactions, because they
often come up as a part of thermochemistry calculations. Don't try to learn the equations - there are far
too many possibilities. Work them out as you need them.

Example:
1. C3H6 + 4½O2  3CO2 + 3H2O

Or you can multiply each term by 2 to remove the fraction:

2C3H6 + 9O2  6CO2 + 6H2O

2. C4H8 + 4O2  4CO2 + 4H2O

Trends
The hydrocarbons become harder to burn as the molecules get bigger. This is because the bigger
molecules don't vaporise so easily - the reaction is much better if the oxygen and the hydrocarbon are well
mixed as gases. If the liquid isn't very volatile, only those molecules on the surface can react with the
oxygen. Bigger molecules have greater Van der Waals attractions which make it more difficult for them to
break away from their neighbours and turn to a gas. Provided the combustion is complete, all the
hydrocarbons will burn with a blue flame. However, combustion tends to be less complete as the number
of carbon atoms in the molecules rises. That means that the bigger the hydrocarbon, the more likely you
are to get a yellow, smoky flame.

Incomplete Combustion
Incomplete combustion (where there isn't enough oxygen present) can lead to the formation of carbon or
carbon monoxide.
As a simple way of thinking about it, the hydrogen in the hydrocarbon gets the first chance at the oxygen,
and the carbon gets whatever is left over!
The presence of glowing carbon particles in a flame turns it yellow, and black carbon is often visible in
the smoke. Carbon monoxide is produced as a colourless poisonous gas.

? Why is carbon monoxide poisonous?

Oxygen is carried around the blood by haemoglobin. Unfortunately carbon monoxide binds to exactly the
same site on the haemoglobin that oxygen does. The difference is that carbon monoxide binds

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irreversibly - making that particular molecule of haemoglobin useless for carrying oxygen. If you breathe
in enough carbon monoxide you will die from a sort of internal suffocation.

12.5.2 The Hydrogenation of Alkenes

This is a reaction of the carbon-carbon double bond in alkenes with hydrogen in the presence of a metal
catalyst. It includes the manufacture of margarine from animal or vegetable fats and oils.

12.5.2.1 The hydrogenation of Ethene

Ethene reacts with hydrogen in the presence of a finely divided nickel catalyst at a temperature of about
150°C. Ethane is produced.

This is a fairly pointless reaction because ethene is a far more useful compound than ethane! However,
what is true of the reaction of the carbon-carbon double bond in ethene is equally true of it in much more
complicated cases.

12.5.2.2 Margarine Manufacture

Some margarine is made by hydrogenating carbon-carbon double bonds in animal or vegetable fats and
oils. You can recognise the presence of this in foods because the ingredients list will include words
showing that it contains "hydrogenated vegetable oils" or "hydrogenated fats". The impression is
sometimes given that all margarine is made by hydrogenation - that's simply not true.

Animal and vegetable fats and oils: these are similar molecules, differing in their melting points. If the
compound is a solid at room temperature, you usually call it a fat. If it is a liquid, it is often described as
oil. Their melting points are largely determined by the presence of carbon-carbon double bonds in the
molecule. The higher the number of carbon-carbon double bonds, the lower the melting point. If there
aren't any carbon-carbon double bonds, the substance is said to be saturated. A typical saturated fat might
have the structure:

Molecules of this sort are usually solid at room temperature. If there is only one carbon-carbon double
bond in each of the hydrocarbon chains, it is called a mono-unsaturated fat (or mono-unsaturated oil,
because it is likely to be a liquid at room temperature.)
A typical mono-unsaturated oil might be:

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If there are two or more carbon-carbon double bonds in each chain, then it is said to be
polyunsaturated. For example:

For simplicity, in all these diagrams, all three hydrocarbon chains in each molecule are the same. That
doesn't have to be the case - you can have a mixture of types of chain in the same molecule.

Making Margarine

Vegetable oils often contain high proportions of polyunsaturated and mono-unsaturated fats (oils), and as
a result are liquids at room temperature. That makes them messy to spread on your bread or toast, and
inconvenient for some baking purposes. You can "harden" (raise the melting point of) the oil by
hydrogenating it in the presence of a nickel catalyst. Conditions (like the precise temperature or the length
of time the hydrogen is passed through the oil) are carefully controlled so that some, but not necessarily
all, of the carbon-carbon double bonds are hydrogenated. This produces a "partially hydrogenated oil" or
"partially hydrogenated fat".
You need to hydrogenate enough of the bonds to give the final texture you want. However, there are
possible health benefits in eating mono-unsaturated or polyunsaturated fats or oils rather than saturated
ones - so you wouldn't want to remove all the carbon-carbon double bonds.
The flow diagram below shows the complete hydrogenation of typical mono-unsaturated oil.

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The downside of hydrogenation as a means of hardening fats and oils

There are some probable health risks from eating hydrogenated fats or oils. Consumers are becoming
more aware of this, and manufacturers are increasingly finding alternative ways of converting oils into
spreadable solids. One of the problems arises from the hydrogenation process. The double bonds in
unsaturated fats and oils tend to have the groups around them arranged in the "cis" form.

The relatively high temperatures used in the hydrogenation process tend to flip some of the carbon-
carbon double bonds into the "trans" form. If these particular bonds aren't hydrogenated during the
process, they will still be present in the final margarine in molecules of trans fats.

The consumption of trans fats has been shown to increase cholesterol levels (particularly of the more
harmful LDL form) - leading to an increased risk of heart disease. Any process which tends to increase
the amount of trans fat in the diet is best avoided. Read food labels, and avoid any food which contains
(or is cooked in) hydrogenated oil or hydrogenated fat.

12.5.3 The Halogenation of Alkenes

12.5.3.1 Simple Reactions Involving Halogens
In each case, we will look at ethene as typical of all of the alkenes. There are no complications as far as
the basic facts are concerned as the alkenes get bigger.

12.5.3.2 Ethene and fluorine

Ethene reacts explosively with fluorine to give carbon and hydrogen fluoride gas. This isn't a useful
reaction, and you aren't likely to need it for exam purposes at this level.

12.5.3.3 Ethene and chlorine or bromine or iodine

In each case you get an addition reaction. For example, bromine adds to give 1,2-dibromoethane.

The reaction with bromine happens at room temperature. If you have a gaseous alkene like ethene, you
can bubble it through either pure liquid bromine or a solution of bromine in an organic solvent like

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tetrachloromethane. The reddish-brown bromine is decolourised as it reacts with the alkene. A liquid
alkene (like cyclohexene) can be shaken with liquid bromine or its solution in tetrachloromethane.
Chlorine reacts faster than bromine, but the chemistry is similar. Iodine reacts much, much more slowly,
but again the chemistry is similar. You are much more likely to meet the bromine case than either of
these.

12.5.4 Alkenes and Bromine Water

Using bromine water as a test for alkenes
If you shake an alkene with bromine water (or bubble a gaseous alkene through bromine water), the
solution becomes colourless.

Alkenes decolourise bromine water

The chemistry of the test

This is complicated by the fact that the major product isn't 1,2-dibromoethane. The water also gets
involved in the reaction, and most of the product is 2-bromoethanol.

However, there will still be some 1,2-dibromoethane formed, so at this sort of level you can probably get
away with quoting the simpler equation:

12.5.5 Reaction of Alkenes and Hydrogen Halides

12.5.5.1 Addition to Symmetrical Alkenes

? What happens?

All alkenes undergo addition reactions with the hydrogen halides. A hydrogen atom joins to one of the
carbon atoms originally in the double bond, and a halogen atom to the other.
For example, with ethene and hydrogen chloride, you get chloroethane:

With but-2-ene you get 2-chlorobutane:

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What happens if you add the hydrogen to the carbon atom at the right-hand end of the double bond, and
the chlorine to the left-hand end? You would still have the same product. The chlorine would be on a
carbon atom next to the end of the chain - you would simply have drawn the molecule flipped over in
space. That would be different if the alkene was unsymmetrical - that's why we have to look at them
separately.

Conditions
The alkenes react with gaseous hydrogen halides at room temperature. If the alkene is also a gas, you can
simply mix the gases. If the alkene is a liquid, you can bubble the hydrogen halide through the liquid.
Alkenes will also react with concentrated solutions of the gases in water. A solution of hydrogen chloride
in water is, of course, hydrochloric acid. A solution of hydrogen bromide in water is hydrobromic acid -
and so on.

There are, however, problems with this. The water will also get involved in the reaction and you end up
with a mixture of products.

? How do you avoid this?

Avoid this problem by using the pure gaseous hydrogen halide.

Reaction Rates
Variation of rates when you change the halogen
Reaction rates increase in the order HF - HCl - HBr - HI. Hydrogen fluoride reacts much more slowly
than the other three, and is normally ignored in talking about these reactions.

When the hydrogen halides react with alkenes, the hydrogen- halogen bond has to be broken. The bond
strength falls as you go from HF to HI, and the hydrogen-fluorine bond is particularly strong. Because it
is difficult to break the bond between the hydrogen and the fluorine, the addition of HF is bound to be
slow.

Variation of rates when you change the alkene

This applies to unsymmetrical alkenes as well as to symmetrical ones. For simplicity the examples given
below are all symmetrical ones- but they don't have to be. Reaction rates increase as the alkene gets more
complicated - in the sense of the number of alkyl groups (such as methyl groups) attached to the carbon
atoms at either end of the double bond.
For example:

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There are two ways of looking at the reasons for this - both of which need you to know about the
mechanism for the reactions. Alkenes react because the electrons in the pi () bond attract things with
any degree of positive charge. Anything which increases the electron density around the double bond will
help this. Alkyl groups have a tendency to "push" electrons away from themselves towards the double
bond. The more alkyl groups you have, the more negative the area around the double bonds becomes.
The more negatively charged that region becomes, the more it will attract molecules like hydrogen
chloride. The more important reason, though, lies in the stability of the intermediate ion formed during
the reaction. The three examples given above produce these carbocations (carbonium ions) at the half-
way stage of the reaction:

The stability of the intermediate ions governs the activation energy for the reaction. As you go towards
the more complicated alkenes, the activation energy for the reaction falls. That means that the reactions
become faster.

Addition to Unsymmetrical Alkenes

? What happens?

In terms of reaction conditions and the factors affecting the rates of the reaction, there is no difference
whatsoever between these alkenes and the symmetrical ones described above. The problem comes with
the orientation of the addition - in other words, which way around the hydrogen and the halogen add
across the double bond.

Orientation of addition
If HCl adds to an unsymmetrical alkene like propene, there are two possible ways it could add. However,
in practice, there is only one major product.

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This is in line with Markovnikov's Rule which says:

Markovnikov’s Rule states that: When a compound HX is added to an

unsymmetrical alkene, the hydrogen becomes attached to the carbon with the
most hydrogen attached to it already (i.e. the hydrogen is attached to the least
substituted carbon and X is attached to the more substituted carbon).

In this case, the hydrogen becomes attached to the CH2 group, because the CH2 group has more
hydrogens than the CH group. Notice that only the hydrogens directly attached to the carbon atoms at
either end of the double bond count. The ones in the CH3 group are totally irrelevant.

12.5.5.3 A special problem with hydrogen bromide

Unlike the other hydrogen halides, hydrogen bromide can add to a carbon-carbon double bond either way
around - depending on the conditions of the reaction.
If the hydrogen bromide and alkene are entirely pure: In this case, the hydrogen bromide adds on
according to Markovnikov's Rule. For example, with propene you would get 2-bromopropane.

the more substituted carbon

CH3CH=CH2

the least substituted carbon

That is exactly the same as the way the other hydrogen halides add.

If the hydrogen bromide and alkene contain traces of organic peroxides: Oxygen from the air tends to
react slowly with alkenes to produce some organic peroxides, and so you don't necessarily have to add

137
them separately. This is therefore the reaction that you will tend to get unless you take care to exclude all
air from the system.
In this case, the addition is the other way around, and you get 1-bromopropane:

This is sometimes described as an anti-Markovnikov addition or as the peroxide effect.

Organic peroxides are excellent sources of free radicals. In the presence of these, the hydrogen bromide
reacts with alkenes using a different (faster) mechanism. For various reasons, this doesn't happen with the
other hydrogen halides. This reaction can also happen in this way in the presence of ultra-violet light of
the right wavelength to break the hydrogen-bromine bond into hydrogen and bromine free radicals.

12.5.6 Oxidation of Alkenes

12.5.6.1 Alkenes and Sulphuric Acid
(i) The reaction with ethene
Alkenes react with concentrated sulphuric acid in the cold to produce alkyl hydrogensulphates. Ethene
reacts to give ethyl hydrogensulphate.

The structure of the product molecule is sometimes written as CH3CH2HSO4, but the version in the
equation is better because it shows how all the atoms are linked up. You may also find it written as
CH3CH2OSO3H. All you need to do is to learn the structure of sulphuric acid. A hydrogen from the
sulphuric acid joins on to one of the carbon atoms, and the rest joins on to the other one. Make sure that
you can see how the structure of the sulphuric acid relates to the various ways of writing the formula for
the product.

(ii) The reaction with propene

This is typical of the reaction with unsymmetrical alkenes. An unsymmetrical alkene has different groups
at either end of the carbon-carbon double bond. If sulphuric acid adds to an unsymmetrical alkene like
propene, there are two possible ways it could add. You could end up with one of two products depending
on which carbon atom the hydrogen attaches itself to. However, in practice, there is only one major
product.

This is in line with Markovnikov's Rule which says:

? State Markovnikov rule

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In this case, the hydrogen becomes attached to the CH2 group, because the CH2 group has more
hydrogens than the CH group. Notice that only the hydrogens directly attached to the carbon atoms at
either end of the double bond count. The ones in the CH3 group are totally irrelevant.

(iii) Using These Reactions to Make Alcohols

Making ethanol
Ethene is passed into concentrated sulphuric acid to make ethyl hydrogensulphate (as above). The
product is diluted with water and then distilled. The water reacts with the ethyl hydrogensulphate to
produce ethanol which distils off.

Making propan-2-ol
More complicated alkyl hydrogensulphates react with water in exactly the same way. For example:

Notice that the position of the -OH group is determined by where the HSO4 group was attached. You get
propan-2-ol rather than propan-1-ol because of the way the sulphuric acid originally added across the
double bond in propene.

12.5.6.2 Alkenes and Potassium Manganate (VII)

Alkenes react with potassium manganate(VII) solution in the cold. The colour change depends on
whether the potassium manganate(VII) is used under acidic or alkaline conditions. If the potassium
manganate(VII) solution is acidified with dilute sulphuric acid, the purple solution becomes colourless. If
the potassium manganate(VII) solution is made slightly alkaline (often by adding sodium carbonate
solution), the purple solution first becomes dark green and then produces a dark brown precipitate.

12.5.7 The Direct Hydration of Alkenes

Direct hydration of alkenes means adding water directly to the carbon-carbon double bond. This will
result into the formation of an alcohol.

12.5.7.1 Direct hydration of ethane to form ethanol

Ethanol is manufactured by reacting ethene with steam. The reaction is reversible.

Only 5% of the ethene is converted into ethanol at each pass through the reactor. By removing the
ethanol from the equilibrium mixture and recycling the ethene, it is possible to achieve an overall 95%
conversion.
A flow scheme for the reaction looks like this:

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 Figure 12.3: Manufacturing of ethanol

12.5.7.2 Direct hydration of Other Alkenes

If you start from an unsymmetrical alkene like propene, you have to be careful to think about which way
around the water adds across the carbon-carbon double bond.

? Recall Markovnikov’s Rule

Thinking of water as H-OH, the hydrogen will add to the carbon with the more hydrogens already
attached. That means that in the propene case, you will get propan-2-ol rather than propan-1-ol.

The conditions used during manufacture vary from alcohol to alcohol. The only conditions you will need
at your level are those for making ethanol.

12.6 General Methods of Preparation of Alkenes

12.6.1 Dehydration of Alcohols Using Aluminium Oxide as Catalyst
(i) The dehydration of ethanol to give ethene
This is a simple way of making gaseous alkenes like ethene. If ethanol vapour is passed over heated
aluminium oxide powder, the ethanol is essentially cracked to give ethene and water vapour.

To make a few test tubes of ethene, you can use this apparatus:

140
Figure 12.4: Preparation of ethene by dehydration of ethanol

It wouldn't be too difficult to imagine scaling this up by boiling some ethanol in a flask and passing the
vapour over aluminium oxide heated in a long tube.

12.6.2 Dehydration of Alcohols Using an Acid Catalyst

The acid catalysts normally used are either concentrated sulphuric acid or concentrated phosphoric(V)
acid, H3PO4. Concentrated sulphuric acid produces messy results. Not only is it an acid, but it is also a
strong oxidising agent. It oxidises some of the alcohol to carbon dioxide and at the same time is reduced
itself to sulphur dioxide. Both of these gases have to be removed from the alkene. It also reacts with the
alcohol to produce a mass of carbon. There are other side reactions as well, but these aren't required by
the foundation syllabus.

(i) The dehydration of ethanol to give ethene

Ethanol is heated with an excess of concentrated sulphuric acid at a temperature of 170°C. The gases
produced are passed through sodium hydroxide solution to remove the carbon dioxide and sulphur
dioxide produced from side reactions. The ethene is collected over water.

The concentrated sulphuric acid is a catalyst. Write it over the arrow rather than in the equation.

Summary
In this Section you have learnt that:
 Hydrocarbons are compounds in which contain Carbon and Hydrogen
atoms only.
 Alkanes are hydrocarbons that contain C-C single bonds and C-H bonds
only, with a general formula CnH2n+2
 Alkanes can undergo some reactions, including combustion and
halogenation.
 Large molecules of Alkanes can undergo cracking to form smaller useful
bits.
 Cracking can be achieved thermally or catalytically.
 Alkanes can be prepared through different methods.
 Alkenes are hydrocarbons that contain carbon=carbon double bonds

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  Alkenes have a general formula CnH2n
 Alkenes may be straight chains or branched chains.
 The smallest alkene is ethene.
 Isomers are different compounds with the same molecular formula
 Alkenes are virtually insoluble in water, but dissolve in organic solvents.
 Alkenes undergo different reactions centred on the C=C double bond,
which are mostly addition in nature.
 Complete combustion of alkenes lead to the formation of carbon dioxide
and water.
 Incomplete combustion of hydrocarbon can lead to the formation of
carbon or carbon monoxide (CO)
 The boiling point of each alkene is very similar to that of the alkane with
the same number of carbon atoms.
 Ethene, Propene and the various Butenes are gases at room temperature
 The important reactions of alkenes all centre around the double bond.
 Hydration of alkenes is a reaction of the carbon-carbon double bond in
alkenes with hydrogen in the presence of a metal catalyst
 All alkenes undergo addition reactions with the hydrogen halides. A
hydrogen atom joins to one of the carbon atoms originally in the double
bond, and a halogen atom to the other. If hcl adds to an unsymmetrical
alkene like propene, there are two possible ways it could add.
 This is in line with Markovnikov's Rule which says when a compound
HX is added to an unsymmetrical alkene, the hydrogen becomes attached
to the carbon with the most hydrogens attached to it already (i.e. the
hydrogen is attached to the least substituted carbon and X is attached to
the more substituted carbon).

Exercise

1. Draw the structures, the three isomers of C5H12 and name them using the IUPAC
system.
2. Using the IUPAC name the following compounds:
CH3
CH3 CH3
(i) CH3CH2CHCHCH3 (ii) (CH3)2CHCH2CHCH3 (iii)
CH2CH3
CH3

3. Draw the structures of cis 2-butene and trans 2-butene.

4. Write a balanced equation to illustrate complete combustion of cyclohexane C 6H12.
5. State the Markovnikov’s Rule for addition of HX to an unsymmetrical alkene eg
butane

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 6. What product would you expect to get when 1-butene reacts with conc. Sulfuric
acid followed by hydrolysis? Write the structure and name the product using
IUPAC system.
7. How would you identify whether a given compound is an alkene or not? Describe
the test that should be done.
8. State the Markovnikov’s Rule for addition of HX to an unsymmetrical alkene e.g.
butane.
9. What product would you expect to get when 1-butene reacts with conc. Sulfuric
acid followed by hydrolysis? Write the structure and name the product using
IUPAC system.
10. How would you identify whether a given compound is an alkene or not? Describe
the test that should be done

References
1. Klein, D. (2012) Organic Chemistry. John Wiley and Sons Inc., Hoboken, US.

2. Loudon, M.G. (2009). Organic Chemistry 5th Edition. Roberts Publishers.

3. McMurry, J. (1995). Organic Chemistry 4th Ed. Pacific Grove. Albany. Boston. Cincinnati. Detroit.
London. Madrid. Melbourne. Mexico City. New York. San Francisco. Singapore. Tokyo.
Toronto. Washington. Brooks/Cole Publishing company

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Lecture 13
Halogenoalkanes (Haloalkanes)

13.1 Introduction
Halogenoalkanes are also known as Haloalkanes or Alkyl Halides. This Module explains what they are
and discusses their physical properties. It also takes an initial look at their chemical reactivity.

Learning Objectives
At the end of this Module you should be able to:

 Define haloalkanes
 Classify haloalkanes into primary, secondary and tertiary haloalkanes
 Describe the physical properties of haloalkanes
 State the factors that influence boiling points of haloalkanes
 State the factors that influence solubility of haloalkanes in water and in
organic solvents
 Write reactions of haloalkanes with different nucleophiles
 Differentiate substitution and elimination reactions of haloalkanes
 State the factors that favour substitution and those that favour
elimination
 Write the general formula of Grignard reagent
 Give the reagents and necessary conditions needed for the preparation of
a Grignard reagent
 Write reactions of Grignard reagents

13.2 Definition of Halogenoalkanes

Halogenoalkanes are compounds in which one or more hydrogen atoms in an alkane have been replaced
by halogen atoms (fluorine, chlorine, bromine or iodine). For the purposes of this course, we will only
look at compounds containing one halogen atom.

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For example:

13.2.1 Classes of Halogenoalkanes

Halogenoalkanes fall into different classes depending on how the halogen atom is positioned on the chain
of carbon atoms. There are some chemical differences between the various types.

13.2.1.1 Primary Halogenoalkanes

In a primary (1°) halogenoalkane, the carbon which carries the halogen atom is only attached to one other
alkyl group.
Some examples of primary halogenoalkanes include:

Notice that it doesn't matter how complicated the attached alkyl group is. In each case there is only one
linkage to an alkyl group from the CH2 group holding the halogen.

There is an exception to this. CH3Br and the other methyl halides are often counted as primary
halogenoalkanes even though there are no alkyl groups attached to the carbon with the halogen on it.

13.2.1.2 Secondary Halogenoalkanes

In a secondary (2°) halogenoalkane, the carbon with the halogen attached is joined directly to two other
alkyl groups, which may be the same or different.
Examples:

13.2.1.3 Tertiary Halogenoalkanes

In a tertiary (3°) halogenoalkane, the carbon atom holding the halogen is attached directly to three alkyl
groups, which may be any combination of same or different.
Examples:

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13.3 Physical Properties of Halogenoalkanes
13.3.1 Boiling Points
The chart shows the boiling points of some simple halogenoalkanes.

Figure 13.1: Boiling points of some simple halogenalkanes

Notice that three of these have boiling points below room temperature (taken as being about 20°C).
These will be gases at room temperature. All the others you are likely to come across are liquids.

The only methyl halide which is a liquid is iodomethane others are gases e.g.
chloroethane is a gas.

The patterns in boiling point reflect the patterns in intermolecular attractions.

Van Der Waals Dispersion Forces

These attractions get stronger as the molecules get longer and have more electrons. That increases the
sizes of the temporary dipoles that are set up. This is why the boiling points increase as the number of
carbon atoms in the chains increases. Look at the chart for a particular type of halide (a chloride, for
example). Dispersion forces get stronger as you go from 1 to 2 to 3 carbons in the chain. It takes more
energy to overcome them, and so the boiling points rise.

The increase in boiling point as you go from a chloride to a bromide to an iodide (for a given number of
carbon atoms) is also because of the increase in number of electrons leading to larger dispersion forces.
There are lots more electrons in, for example, iodomethane than there are in chloromethane - count
them!

Van Der Waals Dipole-Dipole Attractions

The carbon-halogen bonds (apart from the carbon-iodine bond) are polar, because the electron pair is
pulled closer to the halogen atom than the carbon. This is because (apart from iodine) the halogens are
more electronegative than carbon.

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Table 13.1: Electronegativities of halogens compared to carbon
C 2.5 F 4.0
Cl 3.0
Br 2.8
I 2.5

This means that in addition to the dispersion forces there will be forces due to the attractions between the
permanent dipoles (except in the iodide case). The size of those dipole-dipole attractions will fall as the
bonds get less polar (as you go from chloride to bromide to iodide, for example). Nevertheless, the
boiling points rise! This shows that the effect of the permanent dipole-dipole attractions is much less
important than that of the temporary dipoles which cause the dispersion forces. The large increase in
number of electrons by the time you get to the iodide completely outweighs the loss of any permanent
dipoles in the molecules.

Boiling points of some isomers

The examples show that the boiling points fall as the isomers go from a primary to a secondary to a
tertiary halogenoalkane. This is a simple result of the fall in the effectiveness of the dispersion forces. The
temporary dipoles are greatest for the longest molecule. The attractions are also stronger if the molecules
can lie closely together. The tertiary halogenoalkane is very short and fat, and won't have much close
contact with its neighbours.

13.3.2 Solubility of Halogenoalkanes

13.3.2.1 Solubility in water

The halogenoalkanes are at best only very slightly soluble in water. In order for a halogenoalkane to
dissolve in water you have to break attractions between the halogenoalkane molecules (van der Waals
dispersion and dipole-dipole interactions) and break the hydrogen bonds between water molecules. Both
of these cost energy. Energy is released when new attractions are set up between the halogenoalkane and
the water molecules. These will only be dispersion forces and dipole-dipole interactions. These aren't as
strong as the original hydrogen bonds in the water, and so not as much energy is released as was used to
separate the water molecules. The energetics of the change are sufficiently "unprofitable" that very little
dissolves.

13.3.2.2 Solubility in organic solvents

Halogenoalkanes tend to dissolve in organic solvents because the new intermolecular attractions have
much the same strength as the ones being broken in the separate halogenoalkane and solvent.

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13.4 Chemical Reactivity of Halogenoalkanes
13.4.1 The Importance of Bond Strengths
The pattern in strengths of the four carbon-halogen bonds is:

Figure 13.2: The pattern in strengths of the four carbon-halogen bonds

Notice that bond strength falls as you go from C-F to C-I, and notice how much stronger the carbon-
fluorine bond is than the rest. In order for anything to react with the halogenoalkanes, the carbon-
halogen bond has got to be broken. Because that gets easier as you go from fluoride to chloride to
bromide to iodide, the compounds get more reactive in that order. Iodoalkanes are the most reactive and
fluoroalkanes are the least. In fact, fluoroalkanes are so unreactive that we shall pretty well ignore them
completely from now on in this section!

13.4.2 The Influence of Bond Polarity

Of the four halogens, fluorine is the most electronegative and iodine the least. That means that the
electron pair in the carbon-fluorine bond will be dragged most towards the halogen end. Looking at the
methyl halides as simple examples:

The electronegativities of carbon and iodine are equal and so there will be no separation of charge on the
bond. One of the important set of reactions of halogenoalkanes involves replacing the halogen by
something else - substitution reactions. These reactions involve either: the carbon-halogen bond
breaking to give positive and negative ions. The ion with the positively charged carbon atom then reacts
with something either fully or slightly negatively charged. Something either fully or negatively charged
attracted to the slightly positive carbon atom and pushing off the halogen atom. You might have thought
that either of these would be more effective in the case of the carbon-fluorine bond with the quite large
amounts of positive and negative charge already present. But that's not so - quite the opposite is true! The
thing that governs the reactivity is the strength of the bonds which have to be broken. It is difficult to
break a carbon-fluorine bond, but easy to break a carbon-iodine one.

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13.5 Reactions of Halogenoalkanes
13.5.1 Reactions with Hydroxide Ions
This section looks at the reactions between halogenoalkanes with hydroxide ions from sodium or
potassium hydroxide solutions. It covers both substitution and elimination reactions.

? Substitution or elimination?

There are two different sorts of reaction that you can get depending on the conditions used and the type
of halogenoalkane. Primary, secondary and tertiary halogenoalkanes behave differently in this respect.

13.5.1.1 Substitution Reactions

In a substitution reaction, the halogen atom is replaced by an -OH group to give an alcohol.
For example:

or, as an ionic equation:

In the example, 2-bromopropane is converted into propan-2-ol. The halogenoalkane is heated under
reflux with a solution of sodium or potassium hydroxide. Heating under reflux means heating with a
condenser placed vertically in the flask to prevent loss of volatile substances from the mixture. The
solvent is usually a 50/50 mixture of ethanol and water, because everything will dissolve in that. The
halogenoalkane is insoluble in water. If you used water alone as the solvent, the halogenoalkane and the
sodium hydroxide solution wouldn't mix and the reaction could only happen where the two layers met.

13.5.1.2 Elimination Reactions

Halogenoalkanes also undergo elimination reactions in the presence of sodium or potassium hydroxide.

The 2-bromopropane has reacted to give an alkene - propene. Notice that a hydrogen atom has been
removed from one of the end carbon atoms together with the bromine from the centre one. In all simple
elimination reactions the things being removed are on adjacent carbon atoms, and a double bond is set up
between those carbons. The halogenoalkane is heated under reflux with a concentrated solution of
sodium or potassium hydroxide in ethanol. Propene is formed and, because this is a gas, it passes through
the condenser and can be collected.

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13.5.1.3 What Decides whether you Get Substitution or Elimination?

The reagents you are using are the same for both substitution and elimination - the halogenoalkane and
either sodium or potassium hydroxide solution. In all cases, you will get a mixture of both reactions
happening - some substitution and some elimination. What you get most of depends on a number of
factors.

The type of halogenoalkane

This is the most important factor.

Type of halogenoalkane Substitution or Elimination?

primary mainly substitution

secondary both substitution and elimination

tertiary mainly elimination

For example, whatever you do with tertiary halogenoalkanes, you will tend to get mainly the elimination
reaction, whereas with primary ones you will tend to get mainly substitution. However, you can influence
things to some extent by changing the conditions.

(ii) The solvent

The proportion of water to ethanol in the solvent matters:
Water encourages substitution.
Ethanol encourages elimination.

(iii) The temperature

Higher temperatures encourage elimination.

(iv) Concentration of the sodium or potassium hydroxide solution

Higher concentrations favour elimination.

13.6 Preparation of Grignard Reagent from Halogenoalkanes

13.6.1 What are Grignard Reagents?

? What are Grignard reagents?

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A Grignard reagent has a formula RMgX where X is a halogen, and R is an alkyl or aryl (based on a
benzene ring) group. For the purposes of this page, we shall take R to be an alkyl group. A typical
Grignard reagent might be CH3CH2MgBr.

13.6.2 The Preparation of a Grignard Reagent

Grignard reagents are made by adding the halogenoalkane to small bits of magnesium in a flask
containing ethoxyethane (commonly called diethyl ether or just "ether"). The flask is fitted with a reflux
condenser, and the mixture is warmed over a water bath for 20 - 30 minutes.

Everything must be perfectly dry because Grignard reagents react with water (see below).

Any reactions using the Grignard reagent are carried out with the mixture produced from this reaction.
You can't separate it out in any way.

13.7 Reactions of Grignard Reagent

13.7.1 Grignard Reagents and Water
Grignard reagents react with water to produce alkanes. This is the reason that everything has to be very
dry during the preparation above.
For example:

The inorganic product, Mg(OH)Br, is referred to as a "basic bromide". You can think of it as a sort of
half-way stage between magnesium bromide and magnesium hydroxide.

13.7.2 Grignard Reagents and Carbon dioxide

Grignard reagents react with carbon dioxide in two stages. In the first, you get an addition of the
Grignard reagent to the carbon dioxide. Dry carbon dioxide is bubbled through a solution of the
Grignard reagent in ethoxyethane, made as described above.

For example:

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The product is then hydrolysed (reacted with water) in the presence of a dilute acid. Typically, you would
add dilute sulphuric acid or dilute hydrochloric acid to the solution formed by the reaction with the CO 2.
A carboxylic acid is produced with one more carbon than the original Grignard reagent. The usually
quoted equation is

Almost all sources quote the formation of a basic halide such as Mg(OH)Br as the other product of the
reaction. That's actually misleading because these compounds react with dilute acids. What you end up
with would be a mixture of ordinary hydrated magnesium ions, halide ions and sulphate or chloride ions -
depending on which dilute acid you added.

Grignard Reagents and Carbonyl Compounds

? What are carbonyl compounds?

Carbonyl compounds contain the C=O double bond. The simplest ones have the form:

R and R' can be the same or different, and can be an alkyl group or hydrogen.
If one (or both) of the R groups are hydrogens, the compounds are called aldehydes. For example:

If both of the R groups are alkyl groups, the compounds are called ketones. Examples include:

152
The general reaction between Grignard reagents and carbonyl compounds The reactions between the
various sorts of carbonyl compounds and Grignard reagents can look quite complicated, but in fact they
all react in the same way - all that changes are the groups attached to the carbon-oxygen double bond. It
is much easier to understand what is going on by looking closely at the general case (using "R" groups
rather than specific groups) - and then slotting in the various real groups as and when you need to. The
reactions are essentially identical to the reaction with carbon dioxide - all that differs is the nature of the
organic product. In the first stage, the Grignard reagent adds across the carbon-oxygen double bond:

Dilute acid is then added to this to hydrolyse it. (I am using the normally accepted equation ignoring the
fact that the Mg(OH)Br will react further with the acid.)

An alcohol is formed. One of the key uses of Grignard reagents is the ability to make complicated
alcohols easily.

What sort of alcohol you get depends on the carbonyl compound you started with - in other words, what
R and R' are.

13.7.3.1 The reaction between Grignard reagents and methanal

In methanal, both R groups are hydrogen. Methanal is the simplest possible aldehyde.

Assuming that you are starting with CH3CH2MgBr and using the general equation above, the alcohol you
get always has the form:

Since both R groups are hydrogen atoms, the final product will be:

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A primary alcohol is formed. A primary alcohol has only one alkyl group attached to the carbon atom
with the -OH group on it. You could obviously get a different primary alcohol if you started from a
different Grignard reagent.

13.7.3.2 The reaction between Grignard reagents and other aldehydes

The next biggest aldehyde is ethanal. One of the R groups is hydrogen and the other CH 3.

Again, think about how that relates to the general case. The alcohol formed is:

So this time the final product has one CH3 group and one hydrogen attached.

A secondary alcohol has two alkyl groups (the same or different) attached to the carbon with the -OH
group on it. You could change the nature of the final secondary alcohol by either:

 Changing the nature of the Grignard reagent - which would change the CH3CH2 group into some
other alkyl group;

 Changing the nature of the aldehyde - which would change the CH3 group into some other alkyl
group.

13.7.3.3 The reaction between Grignard reagents and Ketones

Ketones have two alkyl groups attached to the carbon-oxygen double bond. The simplest one is
propanone.

This time when you replace the R groups in the general formula for the alcohol produced you get a
tertiary alcohol.

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A tertiary alcohol has three alkyl groups attached to the carbon with the -OH attached. The alkyl groups
can be any combination of same or different.
You could bring the changes on the product by

 Changing the nature of the Grignard reagent - which would change the CH3CH2 group into some
other alkyl group;

 Changing the nature of the ketone - which would change the CH3 groups into whatever other
alkyl groups you choose to have in the original ketone.

13.7.3.4 Why do Grignard reagents react with carbonyl compounds?

The mechanisms for these reactions aren't required at foundation level syllabuses, but you might need to
know a little about the nature of Grignard reagents. The bond between the carbon atom and the
magnesium is polar. Carbon is more electronegative than magnesium, and so the bonding pair of
electrons is pulled towards the carbon. That leaves the carbon atom with a slight negative charge.

The carbon-oxygen double bond is also highly polar with a significant amount of positive charge on the
carbon atom. The nature of this bond will be described in detail elsewhere as you advance in the course.
This is because of the attraction between the slight negativeness of the carbon atom in the Grignard
reagent and the positiveness of the carbon in the carbonyl compound.

Exercise 13.1
1. Explain why the reactivities of alkyl halides are in the trend shown as we change the
halide: RI >RBr >RCl >RF?
2. In the reaction of alkyl halides with nucleophiles which one is the better nucleophile -
OH or H2O?
3. Write the structure of the Grignard reagent obtained when propyl chloride reacts with
magnesium in dry ether.
4. Write the reaction between ethyl magnesium bromide and acetone followed by
acidification and give the structure of the alcohol expected.
5. Write an equation for the reaction of methyl magnesium iodide with CO 2 and give the
structure of the expected product.

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Lecture 14
Aryl Halides

14.1 Introduction
This Lecture looks at the structure and physical properties of three simple aryl halides - chlorobenzene,
bromobenzene and iodobenzene.

Learning Objectives
At the end of this lecture you should be able to
 Define Aryl Halides
 Give a general structure of an Aryl Halide
 Give structures of three typical examples of Aryl Halides
 Give physical properties of the three common Aryl Halides.

14.2 Definition of Aryl Halides

An aryl halide (also known as haloarene or halogenoarene) is a class of organic compounds containing an
aromatic ring from which a hydrogen atom has been replaced by a halogen atom.
Aromatic rings (also known as aromatic compounds or arenes) are hydrocarbons which contain a ring
structure with C-C single bonds and C=C double bonds. The most common is Benzene (C6H6), which is
a ring of six carbon atoms, with alternating double bonds and single bonds. Benzene can be represented
as:

or or

The aryl halides (halogenoarenes) are distinguished from halogenolkanes we discussed in the Module 13
because they exhibit many differences in methods of preparation and properties.

14.3 Structure of Chlorobenzene

When one hydrogen atom in the benzene ring is replaced by a chlorine atom, the new compound is
chlorobenzene. We'll look in some detail at the structure of chlorobenzene. The structures of
bromobenzene and iodobenzene are just similar to that of chlorobenzene.

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Chlorobenzene

The simplest way to draw the structure of chlorobenzene is:

14.4 Phyisical Properties of Aryl Halides

14.4.1 Boiling Points
Chlorobenzene, bromobenzene and iodobenzene are all oily liquids. The boiling points increase as the
halogen atom gets bigger.

Table 14.1: Boiling points of some Aryl Halides

Boiling point (°C)

Chlorobenzene C6H5Cl 132

Bromobenzene C6H5Br 156

Iodobenzene C6H5I 189

The main attractions between the molecules will be van der Waals dispersion forces. These increase as the
number of electrons in the molecule increases. This is the reason that the boiling points increase as the
halogen atom gets bigger. There will also be permanent dipole-dipole attractions involved in the
chlorobenzene and bromobenzene, but very little in the iodobenzene. Iodine has much the same
electronegativity as carbon.
These dipole-dipole attractions must be very unimportant relative to the dispersion forces because the
most polar molecule (the chlorobenzene) has the lowest boiling point of the three.

14.4.2 Solubility in Water

The aryl halides are insoluble in water. They are denser than water and form a separate lower layer. The
molecules are quite large compared with a water molecule. In order for chlorobenzene to dissolve it
would have to break lots of existing hydrogen bonds between water molecules. You also have to break
the quite strong van der Waals dispersion forces between chlorobenzene molecules. Both of these cost
energy. The only new forces between the chlorobenzene and the water would be van der Waals

157
dispersion forces. These aren't as strong as hydrogen bonds (or the original dispersion forces in the
chlorobenzene), and so you wouldn't get much energy released when they form. It simply isn't
energetically profitable for chlorobenzene (and the others) to dissolve in water.

Summary
In this Lecture you have learnt that:

 An aryl halide has a halogen atom attached directly to a benzene

ring.
 The structure of chlorobenzene, bromobenzene and iodobenzene
are just the same.
 Chlorobenzene, bromobenzene and iodobenzene are all oily liquids.
The boiling points increase as the halogen atom gets bigger.
 The main attractions between the molecules will be van der Waals
dispersion forces
 The aryl halides are insoluble in water. They are denser than water
and form a separate lower layer.

Exercise 14.1
1. What is the major structural difference between alkyl halides and ary halides?
2. Why are aryl halides insoluble in water?

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Lecture 15
Alcohol

15.1 Introduction
This topic explains what alcohols are, and what the difference is between primary, secondary and tertiary
alcohols and their manufacture. It looks in some details at their simple physical properties such as
solubility and boiling points and their chemical reactions.

Learning Objectives
At the end of this topic you should be able to:

 Define an alcohol
 Give a general formula of an alcohol
 Classify alcohols
 Distinguish between primary, secondary and tertiary alcohols using
known standard tests.
 Give physical properties of alcohols
 Write equations for the manufacture of alcohols
 Write equations for different reactions of alcohols
 Write reactions for ester formation from reaction of alcohols and
carboxylic acids

15.2 Definition of Alcohols

Alcohols are compounds in which one or more hydrogen atoms in an alkane have been replaced by an -
OH group. For the purposes of this course, we will only look at compounds containing one -OH group.

Example:

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15.3 Classification of Alcohols
Alcohols fall into different classes depending on how the -OH group is positioned on the chain of carbon
atoms. There are some chemical differences between the various types.

15.3.1 Primary Alcohols

In a primary (1°) alcohol, the carbon which carries the -OH group is only attached to one alkyl group.
Some examples of primary alcohols include:

Notice that it doesn't matter how complicated the attached alkyl group is. In each case there is only one
linkage to an alkyl group from the CH2 group holding the -OH group.

There is an exception to this. Methanol, CH3OH, is counted as a primary alcohol even though there are
no alkyl groups attached to the carbon with the -OH group on it.

15.3.2 Secondary Alcohols

In a secondary (2°) alcohol, the carbon with the -OH group attached is joined directly to two alkyl
groups, which may be the same or different.
Examples:

15.3.3 Tertiary Alcohols

In a tertiary (3°) alcohol, the carbon atom holding the -OH group is attached directly to three alkyl
groups, which may be any combination of same or different.
Examples:

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15.4 Phyiscal Properties of Alcohols
15.4.1 Boiling Points
The chart shows the boiling points of some simple primary alcohols with up to 4 carbon atoms.
They are:

They are compared with the equivalent alkane (methane to butane) with the same number of carbon
atoms.

Fig. 15.1: Boiling points of alcohols compared with alkanes

Note that:

 The boiling point of alcohol is always much higher than that of the alkane with
the same number of carbon atoms

 The boiling points of alcohols increase as the number of carbon atoms increases

 The patterns in boiling points reflect the patterns in intermolecular attractions

15.4.2 Hydrogen Bonding

Hydrogen bonding occurs between molecules where you have a hydrogen atom attached to one of the
very electronegative elements - fluorine, oxygen or nitrogen.
In the case of alcohols, there are hydrogen bonds set up between the slightly positive hydrogen atoms and
lone pairs on oxygens in other molecules.

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The hydrogen atoms are slightly positive because the bonding electrons are pulled away from them
towards the very electronegative oxygen atoms. In alkanes, the only intermolecular forces are van der
Waals dispersion forces. Hydrogen bonds are much stronger than these and therefore it takes more
energy to separate alcohol molecules than it does to separate alkane molecules. That's the main reason
that the boiling points are higher.

15.4.3 The Effect of van der Waals Forces

. . . on the boiling points of the alcohols: Hydrogen bonding isn't the only intermolecular force in
alcohols. There are also van der Waals dispersion forces and dipole-dipole interactions. The hydrogen
bonding and the dipole-dipole interactions will be much the same for all the alcohols, but the dispersion
forces will increase as the alcohols get bigger. These attractions get stronger as the molecules get longer
and have more electrons. That increases the sizes of the temporary dipoles that are set up. This is why the
boiling points increase as the number of carbon atoms in the chains increases. It takes more energy to
overcome the dispersion forces, and so the boiling points rise.

on the comparison between alkanes and alcohols:

Even if there wasn't any hydrogen bonding or dipole-dipole interactions, the boiling point of the alcohol
would be higher than the corresponding alkane with the same number of carbon atoms.
Compare ethane and ethanol:

Ethanol is a longer molecule, and the oxygen brings with it an extra 8 electrons. Both of these will
increase the size of the van der Waals dispersion forces and so the boiling point. If you were doing a
really fair comparison to show the effect of the hydrogen bonding on boiling point it would be better to
compare ethanol with propane rather than ethane. The length would then be much the same, and the
number of electrons is exactly the same.

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15.4.4 Solubility of Alcohols in Water
The small alcohols are completely soluble in water. Whatever proportions you mix them in, you will get a
single solution. However, solubility falls as the length of the hydrocarbon chain in the alcohol increases.
Once you get to four carbons and beyond, the fall in solubility is noticeable, and you may well end up
with two layers in your test tube.

15.4.4.1 The solubility of the small alcohols in water

Consider ethanol as a typical small alcohol. In both pure water and pure ethanol the main intermolecular
attractions are hydrogen bonds.

In order to mix the two, you would have to break the hydrogen bonds between the water molecules and
the hydrogen bonds between the ethanol molecules. It needs energy to do both of these things. However,
when the molecules are mixed, new hydrogen bonds are made between water molecules and ethanol
molecules.

The energy released when these new hydrogen bonds are made more or less compensates for that needed
to break the original ones. In addition, there is an increase in the disorder of the system - an increase in
entropy. That is another factor in deciding whether things happen or not.

15.4.4.2 The lower solubility of bigger alcohols

Imagine what happens when you have got, say, 5 carbon atoms in each alcohol molecule.

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The hydrocarbon chains are forcing their way between water molecules and so breaking hydrogen bonds
between those water molecules. The -OH end of the alcohol molecules can form new hydrogen bonds
with water molecules, but the hydrocarbon "tail" doesn't form hydrogen bonds. That means that quite a
lot of the original hydrogen bonds being broken aren't replaced by new ones. All you get in place of those
original hydrogen bonds are van der Waals dispersion forces between the water and the hydrocarbon
"tails".
These attractions are much weaker. That means that you don't get enough energy back to compensate for
the hydrogen bonds being broken. Even allowing for the increase in disorder, the process becomes less
feasible. As the length of the alcohol increases, this situation just gets worse, and so the solubility falls.

15.5 Manufacture of Alcohols

This part of the topic looks at the manufacture of alcohols by the direct hydration of alkenes,
concentrating mainly on the hydration of ethene to make ethanol. It then compares that method with
making ethanol by fermentation.

15.5.1 Manufacturing Alcohols from Alkenes

(i) The manufacture of ethanol from ethene
Ethanol is manufactured by reacting ethene with steam. The catalyst used is solid silicon dioxide coated
with phosphoric(V) acid. The reaction is reversible.

Only 5% of the ethene is converted into ethanol at each pass through the reactor. By removing the
ethanol from the equilibrium mixture and recycling the ethene, it is possible to achieve an overall 95%
conversion. A flow scheme for the reaction looks like this:

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Figure 15.2: Manufacture of ethanol from ethene

15.5.2 The manufacture of Other Alcohols from Alkenes

Some - but not all - other alcohols can be made by similar reactions. The catalyst used and the reaction
conditions will vary from alcohol to alcohol. The only set of conditions you are going to need at your
level are those given above for manufacturing ethanol.
The reason that there is a problem with some alcohols is well illustrated with trying to make an alcohol
from propene, CH3CH=CH2. In principle, there are two different alcohols which might be formed:

You might expect to get either propan-1-ol or propan-2-ol depending on which way around the water
adds to the double bond. In practice what you get is propan-2-ol.

If you add a molecule H-X across a carbon-carbon double bond, the hydrogen nearly always gets attached
to the carbon with the most hydrogens on it already - in this case the CH2 rather than the CH. The effect
of this is that there are bound to be some alcohols which it is impossible to make by reacting alkenes with
steam because the addition would be the wrong way around.

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15.6 Making Ethanol by Fermentation
This method only applies to ethanol. You can't make any other alcohol this way.

15.6.1 The Process

The starting material for the process varies widely, but will normally be some form of starchy plant
material such as maize, wheat, barley or potatoes.
Starch is a complex carbohydrate, and other carbohydrates can also be used - for example, in the
laboratory sucrose (sugar) is normally used to produce ethanol. Industrially, this wouldn't make sense. It
would be silly to refine sugar if all you were going to use it for fermentation. There is no reason why you
shouldn't start from the original sugar cane, though.
The first step is to break complex carbohydrates into simpler ones.
For example, if you were starting from starch in grains like wheat or barley, the grain is heated with hot
water to extract the starch and then warmed with malt. Malt is germinated barley which contains enzymes
which break the starch into a simpler carbohydrate called maltose, C 12H22O11. Maltose has the same
molecular formula as sucrose but contains two glucose units joined together, whereas sucrose contains
one glucose and one fructose unit. Yeast is then added and the mixture is kept warm (say 35°C) for
perhaps several days until fermentation is complete. Air is kept out of the mixture to prevent oxidation of
the ethanol produced to ethanoic acid (vinegar). Enzymes in the yeast first convert carbohydrates like
maltose or sucrose into even simpler ones like glucose and fructose, both C 6H12O6, and then convert
these in turn into ethanol and carbon dioxide. You can show these changes as simple chemical equations,
but the biochemistry of the reactions is much, much more complicated than this suggests.

Yeast is killed by ethanol concentrations in excess of about 15%, and that limits the purity of the ethanol
that can be produced. The ethanol is separated from the mixture by fractional distillation to give 96%
pure ethanol. For theoretical reasons, it is impossible to remove the last 4% of water by fractional
distillation.

Table 15.1: A comparison of fermentation with the direct hydration of ethene

Fermentation Hydration of ethene

Type of A batch process. Everything is put into a
process container and then left until fermentation
is complete. That batch is then cleared out
and a new reaction set up. This is
inefficient.
A continuous flow process. A stream
of reactants is passed continuously
over a catalyst. This is a more efficient
way of doing things.

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 Rate of Very slow. Very rapid.
reaction

Quality of Produces very impure ethanol which needs Produces much purer ethanol.
product further processing

Reaction Uses gentle temperatures and atmospheric Uses high temperatures and pressures,
conditions pressure. needing lots of energy input.

Use of Uses renewable resources based on plant Uses finite resources based on crude
resources material. oil.

15.7 Reactions of Alcohols

15.7.1 Dehydration of Alcohols
This section looks at the dehydration of alcohols in the laboratory to make alkenes - for example,
dehydrating ethanol to make ethene.

Dehydration of Alcohols using Aluminium Oxide as Catalyst

The dehydration of ethanol to give ethene

This is a simple way of making gaseous alkenes like ethene. If ethanol vapour is passed over heated
aluminium oxide powder, the ethanol is essentially cracked to give ethene and water vapour.

To make a few test tubes of ethene, you can use this apparatus:

Figure 15.3: Preparation of ethene from the dehydration of ethanol

It wouldn't be too difficult to imagine scaling this up by boiling some ethanol in a flask and passing the
vapour over aluminium oxide heated in a long tube.

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Dehydration of Alcohols using an Acid Catalyst

The acid catalysts normally used are either concentrated sulphuric acid or concentrated phosphoric(V)
acid, H3PO4. Concentrated sulphuric acid produces messy results. Not only is it an acid, but it is also a
strong oxidising agent. It oxidises some of the alcohol to carbon dioxide and at the same time is reduced
itself to sulphur dioxide. Both of these gases have to be removed from the alkene. It also reacts with the
alcohol to produce a mass of carbon. There are other side reactions as well, but these aren't required by
the Foundation syllabus.

The dehydration of ethanol to give ethene

Ethanol is heated with an excess of concentrated sulphuric acid at a temperature of 170°C. The gases
produced are passed through sodium hydroxide solution to remove the carbon dioxide and sulphur
dioxide produced from side reactions.
The ethene is collected over water

The concentrated sulphuric acid is a catalyst. Write it over the arrow rather than in the equation.

? Why is conc. H2SO4 written over the arrow and not in the
equation?

The dehydration of cyclohexanol to give cyclohexene

This is a preparation commonly used at this level to illustrate the formation and purification of a liquid
product. The fact that the carbon atoms happen to be joined in a ring makes no difference whatever to
the chemistry of the reaction.
Cyclohexanol is heated with concentrated phosphoric(V) acid and the liquid cyclohexene distils off and
can be collected and purified. Phosphoric(V) acid tends to be used in place of sulphuric acid because it is
safer and produces a less messy reaction.

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15.7.2 Reaction of Alcohols with Sodium
This section describes the reaction between alcohols and metallic sodium, and takes a very brief look at
the properties of the alkoxide which is formed. We will look at the reaction between sodium and ethanol
as being typical, but you could substitute any other alcohol you wanted to - the reaction would be the
same.

15.7.2.1 The Reaction between Sodium and Ethanol

Details of the reaction

If a small piece of sodium is dropped into some ethanol, it reacts steadily to give off bubbles of hydrogen
gas and leaves a colourless solution of sodium ethoxide, CH3CH2ONa. Sodium ethoxide is known as an
alkoxide. If the solution is evaporated carefully to dryness, the sodium ethoxide is left as a white solid.

Although at first sight you might think this was something new and complicated, in fact it is exactly the
same (apart from being a more gentle reaction) as the reaction between sodium and water - something
you have probably known about for years.
Compare the two:

We normally, of course, write the sodium hydroxide formed as NaOH rather than HONa - but that's the
only difference. Sodium ethoxide is just like sodium hydroxide, except that the hydrogen has been
replaced by an ethyl group. Sodium hydroxide contains OH - ions; sodium ethoxide contains CH3CH2O-
ions.
Using the reaction
There are two simple uses for this reaction:

To dispose of small amounts of sodium safely

If you spill some sodium on the bench, or have a small amount left over from a reaction, you can't just
chuck it in the sink. It tends to react explosively with the water - and comes flying back out at you again!
It reacts much more gently with ethanol. Ethanol is therefore used to dissolve small quantities of waste
sodium. The solution formed can be washed away without problems (provided you remember that
sodium ethoxide is strongly alkaline - see below).

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To test for the -OH group in alcohols

Because of the dangers involved in handling sodium, this is not the best test for an alcohol at this level.
Because sodium reacts violently with acids to produce a salt and hydrogen, you would first have to be
sure that the liquid you were testing was neutral.

You would also have to be confident that there was no trace of water present because sodium reacts with
the -OH group in water even better than with the one in an alcohol.

With those provisos, if you add a tiny piece of sodium to a neutral liquid free of water and get bubbles of
hydrogen produced, then the liquid is an alcohol.

Some simple reactions of alkoxide ions

This is going beyond the demands of the foundation course syllabus, but you might come across the first
example as a part of a bit of practical work. The second example is to reinforce the similarity between
sodium ethoxide and sodium hydroxide. Once again we will take the ethoxide ions in sodium ethoxide as
typical. Essentially, ethoxide (and other alkoxide) ions behave like hydroxide ions.

Ethoxide ions are strongly basic

If you add water to sodium ethoxide, it dissolves to give a colourless solution with a high pH - typically
pH 14. The solution is strongly alkaline. The reason is that the ethoxide ions remove hydrogen ions from
water molecules to produce hydroxide ions. It is these which produce the high pH.

Ethoxide ions are good nucleophiles

A nucleophile is something which carries a negative or partial negative charge which it uses to attack
positive centres in other molecules or ions. Hydroxide ions are good nucleophiles, and you may have
come across the reaction between a halogenoalkane (also called a haloalkane or alkyl halide) and sodium
hydroxide solution. The hydroxide ions replace the halogen atom.

In this case, an alcohol is formed.

The ethoxide ion behaves in exactly the same way. If you knew the mechanism for the hydroxide ion
reaction you could work out exactly what happens in the reaction between a halogenoalkane and ethoxide
ion.
Compare this equation with the last one.

The only difference is that where there was a hydrogen atom at the right-hand end of the product
molecule, you now have an alkyl group.

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Two alkyl (or other hydrocarbon) groups bridged by an oxygen atom is called an ether. This particular
one is 1-ethoxypropane or ethyl propyl ether. This reaction is a good way of making ethers in the
laboratory.

Replacing the -OH Group in Alcohols by a Halogen

This section looks at reactions in which the -OH group in an alcohol is replaced by a halogen such as
chlorine or bromine. It includes a simple test for an -OH group using phosphorus (V) chloride.

15.7.3 Reactions Involving Hydrogen Halides

The general reaction looks like this:

Reaction with hydrogen chloride

Tertiary alcohols react reasonably rapidly with concentrated hydrochloric acid, but for primary or
secondary alcohols the reaction rates are too slow for the reaction to be of much importance. A tertiary
alcohol reacts if it is shaken with concentrated hydrochloric acid at room temperature. A tertiary
halogenoalkane (haloalkane or alkyl halide) is formed

Replacing -OH by bromine

Rather than using hydrobromic acid, you usually treat the alcohol with a mixture of sodium or potassium
bromide and concentrated sulphuric acid. This produces hydrogen bromide which reacts with the alcohol.
The mixture is warmed to distil off the bromoalkane.

Replacing -OH by iodine

In this case the alcohol is reacted with a mixture of sodium or potassium iodide and concentrated
phosphoric (V) acid, H3PO4, and the iodoalkane is distilled off. The mixture of the iodide and phosphoric
(V) acid produces hydrogen iodide which reacts with the alcohol.

Phosphoric (V) acid is used instead of concentrated sulphuric acid because sulphuric acid oxidises iodide
ions to iodine and produces hardly any hydrogen iodide. A similar thing happens to some extent with
bromide ions in the preparation of bromoalkanes, but not enough to get in the way of the main reaction.

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There is no reason why you couldn't use phosphoric (V) acid in the bromide case instead of sulphuric
acid if you wanted to.

15.7.4 Reacting Alcohols with Phosphorus Halides

Reaction with phosphorus (III) chloride, PCl3
Alcohols react with liquid phosphorus (III) chloride (also called phosphorus trichloride) to make
chloroalkanes.

Reaction with phosphorus (V) chloride, PCl5

Solid phosphorus (V) chloride (phosphorus pentachloride) reacts violently with alcohols at room
temperature, producing clouds of hydrogen chloride gas. It isn't a good choice as a way of making
chloroalkanes, although it is used as a test for -OH groups in organic chemistry.

Phosphorus pentachloride is used as a test for –OH groups in organic

chemistry

To show that a substance was an alcohol, you would first have to eliminate all the other things which also
react with phosphorus (V) chloride. For example, carboxylic acids (containing the -COOH group) react
with it (because of the -OH in -COOH), and so does water (H-OH). If you have a neutral liquid not
contaminated with water, and get clouds of hydrogen chloride when you add phosphorus (V) chloride,
then you have an alcohol group present.

There are also side reactions involving the POCl3 reacting with the alcohol.

Other reactions involving phosphorus halides

Instead of using phosphorus (III) bromide or iodide, the alcohol is usually heated under reflux with a
mixture of red phosphorus and either bromine or iodine. The phosphorus first reacts with the bromine or
iodine to give the phosphorus(III) halide.

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These then react with the alcohol to give the corresponding halogenoalkane which can be distilled off.

15.7.5 Reacting Alcohols with Sulphur Dichloride Oxide (Thionyl Chloride)

The reaction
Sulphur dichloride oxide (thionyl chloride) has the formula SOCl 2.
Traditionally, the formula is written as shown, despite the fact that the modern name writes the chlorine
before the oxygen (alphabetical order SCl 2O). The sulphur dichloride oxide reacts with alcohols at room
temperature to produce a chloroalkane. Sulphur dioxide and hydrogen chloride are given off. Care would
have to be taken because both of these are poisonous.

? Why is this reaction useful?

The big advantage that this reaction has over the use of either of the phosphorus chlorides is that the two
other products of the reaction (sulphur dioxide and HCl) are both gases. That means that they separate
themselves from the reaction mixture.

15.7.6 Oxidation of Alcohols

This section looks at the oxidation of alcohols using acidified sodium or potassium dichromate (VI)
solution. This reaction is used to make aldehydes, ketones and carboxylic acids, and as a way of
distinguishing between primary, secondary and tertiary alcohols.

15.7.6.1 Oxidising the Different Types of Alcohols

The oxidising agent used in these reactions is normally a solution of sodium or potassium dichromate
(VI) acidified with dilute sulphuric acid. If oxidation occurs, the orange solution containing the
dichromate (VI) ions is reduced to a green solution containing chromium (III) ions. The electron-half-
equation for this reaction is:

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1. Primary Alcohols

Primary alcohols can be oxidised to either aldehydes or carboxylic acids depending on the reaction
conditions. In the case of the formation of carboxylic acids, the alcohol is first oxidised to an aldehyde
which is then oxidised further to the acid.

Partial oxidation to aldehydes

You get an aldehyde if you use an excess of the alcohol, and distil off the aldehyde as soon as it forms.
The excess of the alcohol means that there isn't enough oxidising agent present to carry out the second
stage. Removing the aldehyde as soon as it is formed means that it doesn't hang around waiting to be
oxidised anyway! If you used ethanol as a typical primary alcohol, you would produce the aldehyde
ethanal, CH3CHO. The full equation for this reaction is fairly complicated, and you need to understand
about electron-half-equations in order to work it out.

In organic chemistry, simplified versions are often used which concentrate on what is happening to the
organic substances. To do that, oxygen from an oxidising agent is represented as [O]. That would produce
the much simpler equation:

It also helps in remembering what happens. You can draw simple structures to show the relationship
between the primary alcohol and the aldehyde formed.

Full oxidation to carboxylic acids

You need to use an excess of the oxidising agent and make sure that the aldehyde formed as the half-way
product stays in the mixture. The alcohol is heated under reflux with an excess of the oxidising agent.
When the reaction is complete, the carboxylic acid is distilled off. The full equation for the oxidation of
ethanol to ethanoic acid is:

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The more usual simplified version looks like this:

Alternatively, you could write separate equations for the two stages of the reaction - the formation of
ethanal and then its subsequent oxidation.

This is what is happening in the second stage:

2. Secondary alcohols

Secondary alcohols are oxidised to ketones - and that's it. For example, if you heat the secondary alcohol
propan-2-ol with sodium or potassium dichromate (VI) solution acidified with dilute sulphuric acid, you
get propanone formed. Playing around with the reaction conditions makes no difference whatsoever to
the product. Using the simple version of the equation and showing the relationship between the
structures:

If you look back at the second stage of the primary alcohol reaction, you will see that an oxygen "slotted
in" between the carbon and the hydrogen in the aldehyde group to produce the carboxylic acid. In this
case, there is no such hydrogen - and the reaction has nowhere further to go.

3. Tertiary alcohols

Tertiary alcohols aren't oxidised by acidified sodium or potassium dichromate (VI) solution. There is no
reaction whatsoever. If you look at what is happening with primary and secondary alcohols, you will see
that the oxidising agent is removing the hydrogen from the -OH group, and a hydrogen from the carbon
atom attached to the -OH. Tertiary alcohols don't have a hydrogen atom attached to that carbon. You

175
need to be able to remove those two particular hydrogen atoms in order to set up the carbon-oxygen
double bond.

15.7.6.2 Using these Reactions as a Test for the Different Types of Alcohol

(i) Doing the test

First you have to be sure that you have actually got an alcohol by testing for the -OH group. You would
need to show that it was a neutral liquid, free of water and that it reacted with solid phosphorus (V)
chloride to produce a burst of acidic steamy hydrogen chloride fumes. You would then add a few drops
of the alcohol to a test tube containing potassium dichromate (VI) solution acidified with dilute sulphuric
acid. The tube would be warmed in a hot water bath.

(ii) Results for the Various Kinds of Alcohol

Picking out the tertiary alcohol

In the case of a primary or secondary alcohol, the orange solution turns green. With a tertiary alcohol
there is no colour change. After heating:

Distinguishing between the primary and secondary alcohols

You need to produce enough of the aldehyde (from oxidation of a primary alcohol) or ketone (from a
secondary alcohol) to be able to test them. There are various things which aldehydes do which ketones
don't. These include the reactions with Tollens' reagent, Fehling's solution and Benedict's solution.
Experience has shown that, these tests can be a bit of a bother to carry out and the results aren't always as
clear-cut as the books say. A much simpler but fairly reliable test is to use Schiff's reagent.

Schiff's reagent is a fuchsin dye decolourised by passing sulphur dioxide through it. In the presence of
even small amounts of an aldehyde, it turns bright magenta. It must, however, be used absolutely cold,
because ketones react with it very slowly to give the same colour. If you heat it, obviously the change is
faster - and potentially confusing. While you are warming the reaction mixture in the hot water bath, you
can pass any vapours produced through some Schiff's reagent.

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 Figure 15.4: Use of Schiff’s reagent to test for aldehydes

 If the Schiff's reagent quickly becomes magenta, then you are producing an aldehyde from a
primary alcohol.

 If there is no colour change in the Schiff's reagent, or only a trace of pink colour within a minute
or so, then you aren't producing an aldehyde, and so haven't got a primary alcohol. Because of
the colour change to the acidified potassium dichromate (VI) solution, you must therefore have a
secondary alcohol.
You should check the result as soon as the potassium dichromate (VI) solution turns green - if you leave
it too long, the Schiff's reagent might start to change colour in the secondary alcohol case as well.

15.8 Esterification of Alcohols

This section looks at esterification - mainly the reaction between alcohols and carboxylic acids to make
esters. It also looks briefly at making esters from the reactions between acyl chlorides (acid chlorides) and
alcohols, and between acid anhydrides and alcohols.

15.8.1 Definition of Esters

Esters are derived from carboxylic acids. A carboxylic acid contains the -COOH group, and in an ester
the hydrogen in this group is replaced by a hydrocarbon group of some kind. We shall just be looking at
cases where it is replaced by an alkyl group, but it could equally well be an aryl group (one based on a
benzene ring).
(i) A common ester - ethyl ethanoate
The most commonly discussed ester is ethyl ethanoate. In this case, the hydrogen in the -COOH group
has been replaced by an ethyl group. The formula for ethyl ethanoate is:

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Notice that the ester is named the opposite way around from the way the formula is written. The
"ethanoate" bit comes from ethanoic acid. The "ethyl" bit comes from the ethyl group on the end.

(ii) A few more esters

In each case, be sure that you can see how the names and formulae relate to each other.

Notice that the acid is named by counting up the total number of carbon atoms in the chain - including the
one in the -COOH group. So, for example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the
propanoate group.

15.8.2 Making Esters from Carboxylic Acids and Alcohols

(i) The chemistry of the reaction
Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst.
The catalyst is usually concentrated sulphuric acid. Dry hydrogen chloride gas is used in some cases, but
these tend to involve aromatic esters (ones containing a benzene ring). If you are a UK A level student
you won't have to worry about these.
The esterification reaction is both slow and reversible. The equation for the reaction between an acid
RCOOH and an alcohol R'OH (where R and R' can be the same or different) is:

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So, for example, if you were making ethyl ethanoate from ethanoic acid and ethanol, the equation would
be:

(ii) Doing the reactions

On a test tube scale
Carboxylic acids and alcohols are often warmed together in the presence of a few drops of concentrated
sulphuric acid in order to observe the smell of the esters formed. You would normally use small quantities
of everything heated in a test tube stood in a hot water bath for a couple of minutes. Because the
reactions are slow and reversible, you don't get a lot of ester produced in this time. The smell is often
masked or distorted by the smell of the carboxylic acid. A simple way of detecting the smell of the ester is
to pour the mixture into some water in a small beaker.
Apart from the very small ones, esters are fairly insoluble in water and tend to form a thin layer on the
surface. Excess acid and alcohol both dissolve and are tucked safely away under the ester layer. Small
esters like ethyl ethanoate smell like typical organic solvents (ethyl ethanoate is a common solvent in, for
example, glues). As the esters get bigger, the smells tend towards artificial fruit flavouring - "pear drops",
for example.

On a larger scale
If you want to make a reasonably large sample of an ester, the method used depends to some extent on
the size of the ester. Small esters are formed faster than bigger ones. To make a small ester like ethyl
ethanoate, you can gently heat a mixture of ethanoic acid and ethanol in the presence of concentrated
sulphuric acid, and distil off the ester as soon as it is formed. This prevents the reverse reaction
happening. It works well because the ester has the lowest boiling point of anything present. The ester is
the only thing in the mixture which doesn't form hydrogen bonds, and so it has the weakest
intermolecular forces. Larger esters tend to form more slowly. In these cases, it may be necessary to heat
the reaction mixture under reflux for some time to produce an equilibrium mixture. The ester can be
separated from the carboxylic acid, alcohol, water and sulphuric acid in the mixture by fractional
distillation.

15.8.3 Other Ways of Making Esters

Esters can also be made from the reactions between alcohols and either acyl chlorides or acid anhydrides.

15.8.3.1 Making esters from alcohols and acyl chlorides (acid chlorides)

If you add an acyl chloride to an alcohol, you get a vigorous (even violent) reaction at room temperature
producing an ester and clouds of steamy acidic fumes of hydrogen chloride. For example, if you add the
liquid ethanoyl chloride to ethanol, you get a burst of hydrogen chloride produced together with the
liquid ester ethyl ethanoate.

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15.8.3.2 Making esters from alcohols and acid anhydrides

The reactions of acid anhydrides are slower than the corresponding reactions with acyl chlorides, and you
usually need to warm the mixture.
Taking ethanol reacting with ethanoic anhydride as a typical reaction involving an alcohol:
There is a slow reaction at room temperature (or faster on warming). There is no visible change in the
colourless liquids, but a mixture of ethyl ethanoate and ethanoic acid is formed.

Summary
In this topic you have learnt that

 Alcohols are organic compounds with –OH as a functional group

 The general formula of alcohols in R-OH, where R is an alkyl group

 Alcohols can be classified primary, secondary and tertiary alcohols

depending on the number of carbon atoms attached to the carbon
that carries the hydroxyl group

 The boiling point of alcohol is always much higher than that of the
alkane with the same number of carbon atoms

 The boiling points of alcohols increase as the number of carbon

atoms increases

 The patterns in boiling points reflect the patterns in intermolecular

attractions

 In the case of alcohols, there are hydrogen bonds set up between the
slightly positive hydrogen atoms and lone pairs on oxygens in other
molecules.

 The small alcohols (C1-C4) are completely soluble in water.

 ethanol is manufactured by reacting ethene with steam using

phosphoric acid H3PO4 catalyst coated on solid silicon

 ethanol can also be made by fermentation of starchy material such as

maize, wheat, and potatoes but this method can only be used for
manufacture of ethanol, other alcohols cannot be manufactured by
this method

 Alcohols can be dehydrated in the lab to make alkenes - for example,

dehydrating ethanol to make ethene using aluminium oxide as a
catalyst or acid catalysed (conc. H2SO4 at elevated temperature)

 Sodium metal reacts steadily with ethanol to give off bubbles of

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 hydrogen gas and leaves a colourless solution of sodium ethoxide,
CH3CH2ONa. This reaction is normally used to dispose of small
amounts of sodium metal safely.

 Primary alcohols can be oxidised to either aldehydes or carboxylic

acids depending on the reaction conditions. In the case of the
formation of carboxylic acids, the alcohol is first oxidised to an
aldehyde which is then oxidised further to the acid, secondary
alcohols can be oxidized to ketone while tertiary alcohols cannot be
oxidized. The oxidizing agent is normally potassium dichromate VI
(K2Cr2O7)

 The oxidation of primary and secondary alcohols with potassium

dichromate VI is the basis of picking out tertiary alcohol from the
other two because with primary and secondary alcohols the orange
colour of potassium dichromate changes to green but with tertiary
alcohol there is no colour change

 To distinguish between primary and secondary alcohols we use

Schiff’s reagent on the oxidation products of primary and scondaary
alcohols. Schiff’s reagent gives deep magenta colour with aldehydes
in cold, but with ketones in cold there is no colour change

 Esters are derived from carboxylic acids by replacement of the H in

the carboxyl group (COOH) of the carboxylic acid by an alkyl group
of some kind.

 Esters are produced when carboxylic acids are heated with alcohols
in the presence of an acid catalyst. The catalyst is usually
concentrated sulphuric acid; such esterification process is slow and
reversible.

 Other and better ways of producing esters involve reaction of an

alcohol with acyl halide (RCOCl) or an anhydride R(CO)2O.

 The -OH group in an alcohol can be replaced by a halogen to give

haloalkane and there are a number of methods to achieve this
transformation including reaction with phosphorus III halides PCl 3,
phosphorus V halides (PCl5) and sulfur dioxide chloride SO2Cl
(commonly known as thionyl chloride)

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Lecture 16
Carbonyl Compounds

16.1 Introduction
This topic explains what carbonyl compounds are, and looks at the way their bonding affects their
reactivity. It also considers their simple physical properties such as solubility and boiling points and
explains how aldehydes and ketones are made in the lab by the oxidation of primary and secondary
alcohols.

Learning Objectives
At the end of this topic you should be able to:

 Define carbonyl compounds

 Write the general structure aldehydes and ketones and give typical
examples of each

 Discuss bonding in and the polar nature of the carbonyl group and
reactivity of the carbonyl group

 Describe physical properties of aldehydes and ketones

 Write equations for preparation of aldehydes by oxidation of

primary alcohols

 Write equations for preparation of ketones by oxidation of

secondary alcohols

 Write chemical reactions for the reduction of aldehydes and ketones

using lithium aluminium hydride or sodium borohydride to give
alcohols

16.2 Definition of Carbonyl Compounds

Carbonyl compounds are organic compounds which contain a carbonyl group, that is a carbon-oxygen
double bond C=O, mainly aldehydes and ketones. They are simple in the sense that they don't have other
reactive groups like -OH or -Cl attached directly to the carbon atom in the carbonyl group.

16.2.1 Examples of Aldehydes

In aldehydes, the carbonyl group has a hydrogen atom attached to it together with either

 a second hydrogen atom

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  or, more commonly, a hydrocarbon group which might be an alkyl group or one containing a
benzene ring.
For the purposes of this course, we shall ignore those containing benzene rings.

Notice that these all have exactly the same end to the molecule. All that differs is the complexity of the
other group attached. When you are writing formulae for these, the aldehyde group (the carbonyl group
with the hydrogen atom attached) is always written as -CHO - never as COH. That could easily be
confused with an alcohol. Ethanal, for example, is written as CH 3CHO; methanal as HCHO.

The name counts the total number of carbon atoms in the longest chain - including the one in the
carbonyl group. If you have side groups attached to the chain, notice that you always count from the
carbon atom in the carbonyl group as being number 1.

16.2.2 Examples of Ketones

In ketones, the carbonyl group has two hydrocarbon groups attached. Again, these can be either alkyl
groups or ones containing benzene rings. Again, we'll concentrated on those containing alkyl groups just
to keep things simple.
Notice that ketones never have a hydrogen atom attached to the carbonyl group.

Propanone is normally written CH3COCH3. Notice the need for numbering in the longer ketones. In
pentanone, the carbonyl group could be in the middle of the chain or next to the end - giving either
pentan-3-one or pentan-2-one.

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16.3 Reactivity of Carbonyl Compounds
16.3.1 Bonding in the carbonyl group
Oxygen is far more electronegative than carbon and so has a strong tendency to pull electrons in a
carbon-oxygen bond towards itself. One of the two pairs of electrons that make up a carbon-oxygen
double bond is even more easily pulled towards the oxygen. That makes the carbon-oxygen double bond
very highly polar.

 
C O

16.3.2 Important reactions of the carbonyl group

The slightly positive carbon atom in the carbonyl group can be attacked by nucleophiles. A nucleophile
is a negatively charged ion (for example, a cyanide ion, CN-), or a slightly negatively charged part of a
molecule (for example, the lone pair on a nitrogen atom in ammonia, NH 3). During the reaction, the
carbon-oxygen double bond gets broken. The net effect of all this is that the carbonyl group undergoes
addition reactions, often followed by the loss of a water molecule. This gives a reaction known as
addition-elimination or condensation.
Both aldehydes and ketones contain a carbonyl group. That means that their reactions are very similar in
this respect.

16.3.3 Where aldehydes and ketones differ

An aldehyde differs from a ketone by having a hydrogen atom attached to the carbonyl group. This
makes the aldehydes very easy to oxidise. For example, ethanal, CH 3CHO, is very easily oxidised to either
ethanoic acid, CH3COOH, or ethanoate ions, CH3COO-. Ketones don't have that hydrogen atom and are
resistant to oxidation. They are only oxidised by powerful oxidising agents which have the ability to break
carbon-carbon bonds.

16.4 Phyisical Properties of Carbonyl Compounds

16.4.1 Boiling points
Methanal is a gas (boiling point -21°C), and ethanal has a boiling point of +21°C. That means that ethanal
boils at close to room temperature. The other aldehydes and the ketones are liquids, with boiling points
rising as the molecules get bigger. The size of the boiling point is governed by the strengths of the
intermolecular forces.

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van der Waals dispersion forces
These attractions get stronger as the molecules get longer and have more electrons. That increases the
sizes of the temporary dipoles that are set up. This is why the boiling points increase as the number of
carbon atoms in the chains increases - irrespective of whether you are talking about aldehydes or ketones.
van der Waals dipole-dipole attractions
Both aldehydes and ketones are polar molecules because of the presence of the carbon-oxygen double
bond. As well as the dispersion forces, there will also be attractions between the permanent dipoles on
nearby molecules. That means that the boiling points will be higher than those of similarly sized
hydrocarbons - which only have dispersion forces. It is interesting to compare three similarly sized
molecules. They have similar lengths, and similar (although not identical) numbers of electrons.

Table 16.1: Comparison of boiling points among similar size molecules of alkane, aldehyde and
alcohol

Molecule Type Boiling Point (°C)

CH3CH2CH3 alkane -42

CH3CHO aldehyde +21

CH3CH2OH alcohol +78

Notice that the aldehyde (with dipole-dipole attractions as well as dispersion forces) has a boiling point
higher than the similarly sized alkane which only has dispersion forces.

However, the aldehyde's boiling point isn't as high as the alcohol's. In the alcohol, there is hydrogen
bonding as well as the other two kinds of intermolecular attraction.

Although the aldehydes and ketones are highly polar molecules, they don't have any hydrogen atoms
attached directly to the oxygen, and so they can't hydrogen bond with each other.

16.4.2 Solubility in water

The small aldehydes and ketones are freely soluble in water but solubility falls with chain length. For
example, methanal, ethanal and propanone - the common small aldehydes and ketones - are miscible with
water in all proportions. The reason for the solubility is that although aldehydes and ketones can't
hydrogen bond with themselves, they can hydrogen bond with water molecules. One of the slightly
positive hydrogen atoms in a water molecule can be sufficiently attracted to one of the lone pairs on the
oxygen atom of an aldehyde or ketone for a hydrogen bond to be formed.

185
There will also, of course, be dispersion forces and dipole-dipole attractions between the aldehyde or
ketone and the water molecules. Forming these attractions releases energy which helps to supply the
energy needed to separate the water molecules and aldehyde or ketone molecules from each other before
they can mix together.

As chain lengths increase, the hydrocarbon "tails" of the molecules (all the hydrocarbon bits apart from
the carbonyl group) start to get in the way. By forcing themselves between water molecules, they break
the relatively strong hydrogen bonds between water molecules without replacing them by anything as
good. This makes the process energetically less profitable, and so solubility decreases.

16.5 Making Aldehydes and Ketones

16.5.1 Oxidising Alcohols to Make Aldehydes and Ketones
General
The oxidising agent used in these reactions is normally a solution of sodium or potassium dichromate(VI)
acidified with dilute sulphuric acid. If oxidation occurs, the orange solution containing the dichromate(VI)
ions is reduced to a green solution containing chromium(III) ions.
The net effect is that an oxygen atom from the oxidising agent removes a hydrogen from the -OH group
of the alcohol and one from the carbon to which it is attached.

[O] is often used to represent oxygen coming from an oxidising agent.

R and R' are alkyl groups or hydrogen. They could also be groups containing a benzene ring. If at least
one of these groups is a hydrogen atom, then you will get an aldehyde. If they are both alkyl groups then

186
you get a ketone. If you now think about where they are coming from, you will get an aldehyde if the
starting molecule looks like this:

In other words, if you start from a primary alcohol, you will get an aldehyde.
You will get a ketone if your starting molecule looks like this:

. . . where R and R' are both alkyl groups. Secondary alcohols oxidise to give ketones.

16.5.2 Making Aldehydes

Aldehydes are made by oxidising primary alcohols. There is, however, a problem.
The aldehyde produced can be oxidised further to a carboxylic acid by the acidified potassium dichromate
(VI) solution used as the oxidising agent. In order to stop at the aldehyde, you have to prevent this from
happening.
To stop the oxidation at the aldehyde, you

 use an excess of the alcohol. That means that there isn't enough oxidising agent present to carry out
the second stage and oxidise the aldehyde formed to a carboxylic acid.

 distil off the aldehyde as soon as it forms. Removing the aldehyde as soon as it is formed means that
it doesn't stay in the mixture to be oxidised further.

If you used ethanol as a typical primary alcohol, you would produce the aldehyde ethanal, CH 3CHO
(commonly known as acetaldehyde). The full equation for this reaction is fairly complicated, and you need
to understand about electron-half-equations in order to work it out.

In organic chemistry, simplified versions are often used which concentrate on what is happening to the
organic substances. To do that, oxygen from an oxidising agent is represented as [O].
That would produce the much simpler equation:

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16.5.2.1 From Secondary Alcohols

Secondary alcohols are oxidised to ketones. There is no further reaction which might complicate things.
For example, if you heat the secondary alcohol propan-2-ol with sodium or potassium dichromate (VI)
solution acidified with dilute sulphuric acid, you get propanone formed. Playing around with the reaction
conditions makes no difference whatsoever to the product.
Using the simple version of the equation:

16.6 Reduction of Aldehydes and Ketones

This section looks at the reduction of aldehydes and ketones by two similar reducing agents - lithium
tetrahydridoaluminate (III) (also known as lithium aluminium hydride) and sodium tetrahydridoborate
(III) (sodium borohydride).

16.6.1 Background to the Reactions

The reducing agents
Despite the fearsome names, the structures of the two reducing agents are very simple. In each case, there
are four hydrogens ("tetrahydido") around either aluminium or boron in a negative ion (shown by the
"ate" ending).
The "(III)" shows the oxidation state of the aluminium or boron, and is often left out because these
elements only ever show the +3 oxidation state in their compounds. To make the names shorter, that's
what I shall do for the rest of this page.
The formulae of the two compounds are LiAlH4 and NaBH4.
Their structures are:

In each of the negative ions, one of the bonds is a co-ordinate covalent (dative covalent) bond using the
lone pair on a hydride ion (H-) to form a bond with an empty orbital on the aluminium or boron.

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16.6.2 The Overall Reactions

16.6.2.1 The reduction of an Aldehyde

You get exactly the same organic product whether you use lithium tetrahydridoaluminate (also known as
lithium aluminium hydride) or sodium tetrahydridoborate (commonly known as sodium borohydride).
For example, with ethanal you get ethanol:

Notice that this is a simplified equation - perfectly acceptable to UK and many other A level examiners.
[H] means "hydrogen from a reducing agent".
In general terms, reduction of an aldehyde leads to a primary alcohol.

16.6.2.2 The reduction of a ketone

Again the product is the same whichever of the two reducing agents you use.
For example, with propanone you get propan-2-ol:

Reduction of a ketone leads to a secondary alcohol.

16.6.2.3 Reaction Details

Using lithium tetrahydridoaluminate (lithium aluminium hydride)

Lithium tetrahydridoaluminate is much more reactive than sodium tetrahydridoborate. It reacts violently
with water and alcohols, and so any reaction must exclude these common solvents. The reactions are
usually carried out in solution in a carefully dried ether such as ethoxyethane (diethyl ether). The reaction
happens at room temperature, and takes place in two separate stages.

In the first stage, a salt is formed containing a complex aluminium ion. The following equations show
what happens if you start with a general aldehyde or ketone. R and R' can be any combination of
hydrogen or alkyl groups.

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The product is then treated with a dilute acid (such as dilute sulphuric acid or dilute hydrochloric acid) to
release the alcohol from the complex ion.

The alcohol formed can be recovered from the mixture by fractional distillation.

Using sodium tetrahydridoborate (sodium borohydride)

Sodium tetrahydridoborate is a more gentle (and therefore safer) reagent than lithium
tetrahydridoaluminate. It can be used in solution in alcohols or even solution in water - provided the
solution is alkaline.
There is a problem over describing the reaction conditions, because it seems to be used in so many
different ways. Practical details found from various university sites vary widely, and don't necessarily agree
with what theoretical sources say!

The following method is easier to understand what is going on!

Solid sodium tetrahydridoborate is added to a solution of the aldehyde or ketone in an alcohol such as
methanol, ethanol or propan-2-ol. Depending on which recipe you read, it is either heated under reflux or
left for some time around room temperature. This almost certainly varies depending on the nature of the
aldehyde or ketone.
At the end of this time, a complex similar to the previous one is formed.

In the second stage of the reaction, water is added and the mixture is boiled to release the alcohol from
the complex.

Again, the alcohol formed can be recovered from the mixture by fractional distillation.

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16.7 Reaction of Carbonyl Compounds with Grignard Reagent
This section looks at the reaction of aldehydes and ketones with Grignard reagents to produce potentially
quite complicated alcohols. It is mainly a duplication of the information on these same reactions from a
page on Grignard reagents in the section on properties of halogenoalkanes.

? What are Grignard reagents?

Definition of a Grignard Reagent

Definition of Grignard reagent was presented in Module 13. For revision, a Grignard reagent has a
formula RMgX where X is a halogen, and R is an alkyl or aryl (based on a benzene ring) group. For the
purposes of this section, we shall take R to be an alkyl group. A typical Grignard reagent might be
CH3CH2MgBr.

Reactions of Grignard Reagents with Aldehydes and Ketones

These are reactions of the carbon-oxygen double bond, and so aldehydes and ketones react in exactly the
same way - all that changes are the groups that happen to be attached to the carbon-oxygen double bond.
It is much easier to understand what is going on by looking closely at the general case (using "R" groups
rather than specific groups) - and then slotting in the various real groups as and when you need to. The
"R" groups can be either hydrogen or alkyl in any combination. In the first stage, the Grignard reagent
adds across the carbon-oxygen double bond:

Dilute acid is then added to this to hydrolyse it.

An alcohol is formed. One of the key uses of Grignard reagents is the ability to make complicated
alcohols easily. What sort of alcohol you get depends on the carbonyl compound you started with - in
other words, what R and R' are.

16.7.2.1 The Reaction between Grignard Reagents and Methanal

In methanal, both R groups are hydrogen. Methanal is the simplest possible aldehyde.

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Assuming that you are starting with CH3CH2MgBr and using the general equation above, the alcohol you
get always has the form:

Since both R groups are hydrogen atoms, the final product will be:

A primary alcohol is formed. A primary alcohol has only one alkyl group attached to the carbon atom
with the -OH group on it. You could obviously get a different primary alcohol if you started from a
different Grignard reagent.

16.7.2.2 The reaction between Grignard reagents and other aldehydes

The next biggest aldehyde is ethanal. One of the R groups is hydrogen and the other CH3.

Again, think about how that relates to the general case. The alcohol formed is:

So this time the final product has one CH3 group and one hydrogen attached:

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A secondary alcohol has two alkyl groups (the same or different) attached to the carbon with the -OH
group on it.
You could change the nature of the final secondary alcohol by either:

 changing the nature of the Grignard reagent - which would change the CH3CH2 group into some
other alkyl group;

 changing the nature of the aldehyde - which would change the CH3 group into some other alkyl
group.

The reaction Between Grignard Reagents and Ketones

Ketones have two alkyl groups attached to the carbon-oxygen double bond. The simplest one is
propanone.

This time when you replace the R groups in the general formula for the alcohol produced you get a
tertiary alcohol.

A tertiary alcohol has three alkyl groups attached to the carbon with the -OH attached. The alkyl groups
can be any combination of same or different.
You could bring the changes on the product by

 changing the nature of the Grignard reagent - which would change the CH3CH2 group into some
other alkyl group;

 changing the nature of the ketone - which would change the CH3 groups into whatever other alkyl
groups you choose to have in the original ketone.

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Summary
In this Lecture you have learnt that

 Carbonyl compounds are compounds which contain a carbon-oxygen double

bond (carbonyl group), examples of these are aldehydes and ketones

 In aldehydes, the carbonyl group has a hydrogen atom attached to it together with
either a second hydrogen atom or, more commonly, a hydrocarbon group which
might be an alkyl group or one containing a benzene ring.

 The carbon-oxygen double bond very highly polar.

 
C O

 The slightly positive carbon atom in the carbonyl group can be attacked by
nucleophiles.

 A nucleophile is a negatively charged ion (for example, a cyanide ion, CN -), or a

slightly negatively charged part of a molecule (for example, the lone pair on a
nitrogen atom in ammonia, NH3).

 During the reaction, the carbon-oxygen double bond gets broken.

 The net effect of all this is that the carbonyl group undergoes addition reactions, ,
often followed by the loss of a water molecule. Such a reaction known as
addition-elimination or condensation

 An aldehyde differs from a ketone by having a hydrogen atom attached to the

carbonyl group and aldehydes are more reactive than ketones

 Aldehydes and ketones can both be reduced to alcohols

 Reduction of an aldehydes gives a primary alcohol while that of a ketone gives a

secondary alcohol

Exercise 16.1
1. What is a carbonyl compound?
2. Differentiate between an aldehyde be more reactive than a ketone in most reactions?
3. What is the other name for addition-elimination reaction of aldehydes and ketones?
4. Write a chemical equation to show a reaction between an aldehyde and a Grignard
Reagent.

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Lecture 17
Carboxylic Acids

17.1 Introduction
This Module explains what carboxylic acids are, and looks at their simple physical properties such as
solubility and boiling points. It also looks at ways of making carboxylic acids in the lab by the oxidation of
primary alcohols or aldehydes.

Learning Objectives
At the end of this lecture you should be able to

 Define carboxylic acids

 Write the general structure of carboxylic acids

 Give examples of simple molecules of carboxylic acids (C1 to C4

carboxylic acids).

 Describe formation of carboxylic acids from primary alcohols or

aldehydes.

17.2 Definition of Carboxylic Acids

Carboxylic acids are compounds which contain a -COOH group. For the purposes of this page we shall
just look at compounds where the -COOH group is attached either to a hydrogen atom or to an alkyl
group.
Examples of carboxylic acids

The name counts the total number of carbon atoms in the longest chain - including the one in the -
COOH group. If you have side groups attached to the chain, notice that you always count from the
carbon atom in the -COOH group as being number 1.

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17.2.1 Salts of Carboxylic Acids
Carboxylic acids are acidic because of the hydrogen in the -COOH group. When the acids form salts, this
is lost and replaced by a metal. Sodium ethanoate, for example, has the structure:

Depending on whether or not you wanted to stress the ionic nature of the compound, this would be
simplified to CH3COO- Na+ or just CH3COONa.
Notice:

 The bond between the sodium and the ethanoate is ionic. Don't draw a line between the two
(implying a covalent bond). That's absolutely wrong!

 Although the name is written with the sodium first, the formula is always written in one of the
ways shown. This is something you just have to get used to.

17.3 Physical Properties of Carboxylic Acids

The physical properties (for example, boiling point and solubility) of the carboxylic acids are governed by
their ability to form hydrogen bonds.

17.3.1 Boiling Points

Before we look at carboxylic acids, a reminder about alcohols:
The boiling points of alcohols are higher than those of alkanes of similar size because the alcohols can
form hydrogen bonds with each other as well as van der Waals dispersion forces and dipole-dipole
interactions.
The boiling points of carboxylic acids of similar size are higher still.
For example:

Propan-1-ol CH3CH2CH2OH 97.2°C

Ethanoic acid CH3COOH 118°C

These are chosen for comparison because they have identical relative molecular masses and almost the
same number of electrons (which affects van der Waals dispersion forces).

The higher boiling points of the carboxylic acids are still caused by hydrogen bonding, but operating in a
different way.

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In a pure carboxylic acid, hydrogen bonding can occur between two molecules of acid to produce a dimer.

This immediately doubles the size of the molecule and so increases the van der Waals dispersion forces
between one of these dimers and its neighbours - resulting in a high boiling point.

17.3.2 Solubility in Water

In the presence of water, the carboxylic acids don't dimerise. Instead, hydrogen bonds are formed
between water molecules and individual molecules of acid.
The carboxylic acids with up to four carbon atoms will mix with water in any proportion. When you mix
the two together, the energy released when the new hydrogen bonds form is much the same as is needed
to break the hydrogen bonds in the pure liquids.
The solubility of the bigger acids decreases very rapidly with size. This is because the longer hydrocarbon
"tails" of the molecules get between water molecules and break hydrogen bonds. In this case, these
broken hydrogen bonds are only replaced by much weaker van der Waals dispersion forces.
The energetics of dissolving carboxylic acids in water is made more complicated because some of the acid
molecules actually react with the water rather than just dissolving in it. This is the basis for the acidity of
these compounds and is discussed on another page.

17.4 Making Carboxylic Acids

17.4.1 Oxidising Primary Alcohols or Aldehydes
Chemistry of the reactions

Primary alcohols and aldehydes are normally oxidised to carboxylic acids using potassium dichromate(VI)
solution in the presence of dilute sulphuric acid. During the reaction, the potassium dichromate(VI)
solution turns from orange to green.

The potassium dichromate(VI) can just as well be replaced with sodium dichromate(VI). Because what
matters is the dichromate(VI) ion, all the equations and colour changes would be identical.

Primary alcohols are oxidised to carboxylic acids in two stages - first to an aldehyde and then to the acid.
We often use simplified versions of these equations using "[O]" to represent oxygen from the oxidising
agent.

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The formation of the aldehyde is shown by the simplified equation:

"R" is a hydrogen atom or a hydrocarbon group such as an alkyl group.

The aldehyde is then oxidised further to give the carboxylic acid:

If you start with an aldehyde, you are obviously just doing this second stage.
Starting from the primary alcohol, you could combine these into one single equation to give:

For example, if you were converting ethanol into ethanoic acid, the simplified equation would be:

It is possible that you might want to write proper equations for these reactions rather than these
simplified ones. You can work these out from electron-half-equations. How you do this is described in
detail elsewhere on the site.
The complete equation for the conversion of a primary alcohol to a carboxylic acid is:

. . . or if you were starting from an aldehyde is:

Doing the reactions

It would actually be quite uncommon to make an acid starting from an aldehyde, but very common to
start from a primary alcohol. The conversion of ethanol into ethanoic acid would be a typical example.
The alcohol is heated under reflux with an excess of a mixture of potassium dichromate(VI) solution and
dilute sulphuric acid.
Heating under reflux (heating in a flask with a condenser placed vertically in it) prevents any aldehyde
formed escaping before it has time to be oxidised to the carboxylic acid.

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Using an excess of oxidising agent is to be sure that there is enough oxidising agent present for the
oxidation to go all the way to the carboxylic acid.
When oxidation is complete, the mixture can be distilled. You end up with an aqueous solution of the
acid.

17.5 Carboxylic Acids as Acids

This section looks at the simple reactions of carboxylic acids as acids, including their reactions with
metals, metal hydroxides, carbonates and hydrogencarbonates, ammonia and amines.

The Acidity of the Carboxylic Acids

? Why are carboxylic acids acidic?

Using the definition of an acid as a "substance which donates protons (hydrogen ions) to other things",
the carboxylic acids are acidic because of the hydrogen in the -COOH group.

In solution in water, a hydrogen ion is transferred from the -COOH group to a water molecule. For
example, with ethanoic acid, you get an ethanoate ion formed together with a hydroxonium ion, H 3O+.
This reaction is reversible and, in the case of ethanoic acid, no more than about 1% of the acid has
reacted to form ions at any one time. (This is a rough-and-ready figure and varies with the concentration
of the solution.)
These are therefore weak acids.

This equation is often simplified to:

However, if you are going to use this second equation, you must include state symbols. They imply that
the hydrogen ion is actually attached to a water molecule.

17.5.2 The pH of Carboxylic Acid Solutions

The pH depends on both the concentration of the acid and how easily it loses hydrogen ions from the -
COOH group. Ethanoic acid is typical of the acids where the -COOH group is attached to a simple alkyl
group. Typical lab solutions have pH's in the 2 - 3 range, depending on their concentrations. Methanoic
acid is rather stronger than the other simple acids, and solutions have pH's about 0.5 pH units less than
ethanoic acid of the same concentration.

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17.6 Reactions of Carboxylic Acids
17.6.1 With metals
Carboxylic acids react with the more reactive metals to produce a salt and hydrogen. The reactions are
just the same as with acids like hydrochloric acid, except they tend to be rather slower.
For example, dilute ethanoic acid reacts with magnesium. The magnesium reacts to produce a colourless
solution of magnesium ethanoate, and hydrogen is given off. If you use magnesium ribbon, the reaction is
less vigorous than the same reaction with hydrochloric acid, but with magnesium powder, both are so fast
that you probably wouldn't notice much difference.

Remember that these simple carboxylic acids form ions with a single negative
charge, and that the magnesium ion has two positive charges. In essence, this
is no different from writing the formula for magnesium chloride - except that
with these salts the metal is written at the end of the formula rather than at
the beginning.

17.6.2 With metal hydroxides

These are simple neutralisation reactions and are just the same as any other reaction in which hydrogen
ions from an acid react with hydroxide ions. They are most quickly and easily represented by the equation:

If you mix dilute ethanoic acid with sodium hydroxide solution, for example, you simply get a colourless
solution containing sodium ethanoate. The only sign that a change has happened is that the temperature
of the mixture will have increased. This change could well be represented by the ionic equation above, but
if you want it, the full equation for this particular reaction is:

17.6.3 With carbonates and hydrogencarbonates

In both of these cases, a salt is formed together with carbon dioxide and water. Both are most easily
represented by ionic equations.
For carbonates:

and for hydrogencarbonates:

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If you pour some dilute ethanoic acid onto some white sodium carbonate or sodium hydrogencarbonate
crystals, there is an immediate fizzing as carbon dioxide is produced. You end up with a colourless
solution of sodium ethanoate.
With sodium carbonate, the full equation is:

and for sodium hydrogencarbonate:

There is very little obvious difference in the vigour of these reactions compared with the same reactions
with dilute hydrochloric acid. However, you would notice the difference if you used a slower reaction - for
example with calcium carbonate in the form of a marble chip. With ethanoic acid, you would eventually
produce a colourless solution of calcium ethanoate.

In this case, the marble chip would react noticeably more slowly with ethanoic acid than with
hydrochloric acid.

17.6.4 With ammonia

Ethanoic acid reacts with ammonia in exactly the same way as any other acid does. It transfers a hydrogen
ion to the lone pair on the nitrogen of the ammonia and forms an ammonium ion.

If you mix together a solution of ethanoic acid and a solution of ammonia, you will get a colourless
solution of ammonium ethanoate.

17.6.5 With amines

Amines are compounds in which one or more of the hydrogen atoms in an ammonia molecule have been
replaced by a hydrocarbon group such as an alkyl group. For simplicity, we'll just look at compounds
where only one of the hydrogen atoms has been replaced. These are called primary amines.
Simple primary amines include:

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The small amines are very similar indeed to ammonia in many ways. For example, they smell very much
like ammonia and are just as soluble in water. Because all you have done to an ammonia molecule is swap
a hydrogen for an alkyl group, the lone pair is still there on the nitrogen atom. That means that they will
react with acids (including carboxylic acids) in just the same way as ammonia does. For example, ethanoic
acid reacts with methylamine to produce a colourless solution of the salt methylammonium ethanoate.

However complicated the amine, because all of them have got a lone pair on the nitrogen atom, you
would get the same sort of reaction.

17.7 Esterification of Carboxylic Acids

17.7.1 What are Esters?
Esters have a hydrocarbon group of some sort replacing the hydrogen in the -COOH group of a
carboxylic acid. We shall just be looking at cases where it is replaced by an alkyl group, but it could equally
well be an aryl group (one based on a benzene ring).

17.7.1.1 A common ester - ethyl ethanoate

The most commonly discussed ester is ethyl ethanoate. In this case, the hydrogen in the -COOH group
has been replaced by an ethyl group. The formula for ethyl ethanoate is:

Notice that the ester is named the opposite way around from the way the formula is written. The
"ethanoate" bit comes from ethanoic acid. The "ethyl" bit comes from the ethyl group on the end.

17.7.1.2 A few more esters

In each case, be sure that you can see how the names and formulae relate to each other.

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Remember that the acid is named by counting up the total number of carbon atoms in the chain - including
the one in the -COOH group. So, for example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the
propanoate group.

17.7.2 Making Esters

The chemistry of the reaction
Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst.
The catalyst is usually concentrated sulphuric acid. Dry hydrogen chloride gas is used in some cases, but
these tend to involve aromatic esters (ones containing a benzene ring). If you are a UK A level student
you won't have to worry about these.
The esterification reaction is both slow and reversible. The equation for the reaction between an acid
RCOOH and an alcohol R'OH (where R and R' can be the same or different) is:

So, for example, if you were making ethyl ethanoate from ethanoic acid and ethanol, the equation would
be:

Doing the reactions

On a test tube scale
Carboxylic acids and alcohols are often warmed together in the presence of a few drops of concentrated
sulphuric acid in order to observe the smell of the esters formed.

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You would normally use small quantities of everything heated in a test tube stood in a hot water bath for
a couple of minutes.

Because the reactions are slow and reversible, you don't get a lot of ester produced in this time. The smell
is often masked or distorted by the smell of the carboxylic acid. A simple way of detecting the smell of
the ester is to pour the mixture into some water in a small beaker.

Esters are virtually insoluble in water and tend to form a thin layer on the surface. Excess acid and
alcohol both dissolve and are tucked safely away under the ester layer.

Small esters like ethyl ethanoate smell like typical organic solvents (ethyl ethanoate is a common solvent
in, for example, glues).

As the esters get bigger, the smells tend towards artificial fruit flavouring - "pear drops", for example.

On a larger scale

If you want to make a reasonably large sample of an ester, the method used depends to some extent on
the size of the ester. Small esters are formed faster than bigger ones.

To make a small ester like ethyl ethanoate, you can gently heat a mixture of ethanoic acid and ethanol in
the presence of concentrated sulphuric acid, and distil off the ester as soon as it is formed.

This prevents the reverse reaction happening. It works well because the ester has the lowest boiling point
of anything present. The ester is the only thing in the mixture which doesn't form hydrogen bonds, and
so it has the weakest intermolecular forces.

Larger esters tend to form more slowly. In these cases, it may be necessary to heat the reaction mixture
under reflux for some time to produce an equilibrium mixture. The ester can be separated from the
carboxylic acid, alcohol, water and sulphuric acid in the mixture by fractional distillation.

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Summary
In this Section you have learnt that:

 Halogenoalkanes or Haloalkanes are compounds in which one or more

hydrogen atoms in an alkane have been replaced by halogen atoms (fluorine,
chlorine, bromine or iodine). For the purposes of our course, we will only look
at compounds containing one halogen atom.

 Halogenoalkanes fall into different classes, primary, secondary and tertiary

haloalkanes depending on how the halogen atom is positioned on the chain of
carbon atoms.

 There are some chemical differences between the various types.

 The halogenoalkanes are only very slightly soluble in water.

 Halogenoalkanes tend to dissolve in organic solvents because the new

intermolecular attractions have much the same strength as the ones being
broken in the separate halogenoalkane and solvent.

 The pattern in strengths of the four carbon-halogen bonds is: C-F>C-Cl>C-

Br>C-I

 In order for anything to react with the halogenoalkanes, the carbon-halogen

bond has got to be broken.

 Because that gets easier as you go from fluoride to chloride to bromide to

iodide, the compounds get more reactive in that order.

 The reactivity order of alkyl halides is therefore: RI >RBr >RCl >RF

 haloalkanes undergo substitution and elimination reactions with nucleophiles

 The reagents you are using are the same for both substitution or elimination -
the halogenoalkane and either sodium or potassium hydroxide solution.

 In all cases, you will get a mixture of both reactions happening - some
substitution and some elimination. What you get most of depends on a number
of factors.

 For a given halogenoalkane, to favour elimination rather than substitution, use:

higher temperatures; a concentrated solution of sodium or potassium hydroxide
and pure ethanol as the solvent

 To favour substitution rather than elimination, use: lower temperatures; more

dilute solutions of sodium or potassium hydroxide and more water in the
solvent mixture.

 Grignard reagent has the general formula RMgX where R is an alkyl or aryl
group and X is a halogen. A typical structure of a Grignard reagent is for

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 example CH3CH2MgBr

 Grignard reagents are made by adding the halogenoalkane to small bits of

magnesium in a flask containing dry ethoxyethane (diethyl ether)

 Grignard reagents are sensitive to moisture, they react with water to produce
alkanes. This is the reason that everything has to be very dry during the
preparation of a Grignard reagent

 The major reactions of Grignard reagents are with carbonyl compounds

 Carbonyl compounds contain the C=O double bond. The simplest ones have
the form

 Carboxylic acids are compounds which contain a -COOH group

 Carboxylic acids can be prepared from primary alcohols by by a two –step

oxidation using potassium dichromate VI

 In the presence of water, the carboxylic acids don't dimerise. Instead, hydrogen
bonds are formed between water molecules and individual molecules of acid

 The carboxylic acids with up to four carbon atoms will mix with water in any
proportion.

 The boiling points of carboxylic acids are much higher than those of alcohols
of comparable number of carbon atoms

Exercise 17.1
1. What is the functional group in any carboxylic acid?
2. Name any naturally occurring carboxylic acid?
3. Describe the physical properties of carboxylic acids
4. Why are the boiling points of carboxylic acids higher than corresponding alcohols?
5. Write chemical reactions for formations of carboxylic acids from:
(i) alcohol
(ii) aldehyde

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 Summary
This Section consists of five Lectures. In Lecture 13 we learned that halogenoalkanes also known as
haloalkanes are compounds in which one or more hydrogen atoms in an alkane have been replaced by
halogen atoms (fluorine, chlorine, bromine or iodine). For the purposes of our course, we will only look
at compounds containing one halogen atom. Halogenoalkanes fall into different classes, primary,
secondary and tertiary haloalkanes depending on how the halogen atom is positioned on the chain of
carbon atoms.

The halogenoalkanes are only very slightly soluble in water. Halogenoalkanes tend to dissolve in organic
solvents because the new intermolecular attractions have much the same strength as the ones being
broken in the separate halogenoalkane and solvent.

The pattern in strengths of the four carbon-halogen bonds is: C-F>C-Cl>C-Br>C-I. Order for anything
to react with the halogenoalkanes, the carbon-halogen bond has got to be broken. Because that gets easier
as you go from fluoride to chloride to bromide to iodide, the compounds get more reactive in that order.

The reactivity order of alkyl halides is therefore: ri >rbr >rcl >rf. Haloalkanes undergo substitution and
elimination reactions with nucleophiles.

The reagents you are using are the same for both substitution or elimination – the halogenoalkane and
either sodium or potassium hydroxide solution. In all cases, you will get a mixture of both reactions
happening – some substitution and some elimination. What you get most of depends on a number of
factors.

 For a given halogenoalkane, to favour elimination rather than substitution, use:

(a) Higher temperatures, (b) A concentrated solution of sodium or potassium hydroxide, (c) Pure
ethanol as the solvent,

 To favour substitution rather than elimination, use: (a) Lower temperatures,

(b) More dilute solutions of sodium or potassium hydroxide, (c) More water in the solvent
mixture.

In Leture 14 we learned that an aryl halide is an organic compound that has a halogen atom attached
directly to a benzene ring. There is an interaction between the delocalised electrons in the benzene ring
and one of the lone pairs on the halogen atom. The structure of chlorobenzene, bromobenzene and
iodobenzene are just the same. Chlorobenzene, bromobenzene and iodobenzene are all oily liquids. The
boiling points increase as the halogen atom gets bigger.
The main attractions between the molecules will be van der waals dispersion forces. The aryl halides are
insoluble in water. They are denser than water and form a separate lower layer.
In Lecture 15 we learned that alcohols can be classified primary, secondary and tertiary alcohols
depending on the number of carbon atoms attached to the carbon that carries the hydroxyl group. The
boiling point of alcohol is always much higher than that of the alkane with the same number of carbon
atoms. The boiling points of alcohols increase as the number of carbon atoms increases. The patterns in
boiling points reflect the patterns in intermolecular attractions.

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Hydrogen bonding occurs between molecules where you have a hydrogen atom attached to one of the
very electronegative elements – fluorine, oxygen or nitrogen. In the case of alcohols, there are hydrogen
bonds set up between the slightly positive hydrogen atoms and lone pairs on oxygens in other molecules.
The small alcohols (C1-C4) are completely soluble in water. Ethanol is manufactured by reacting ethene
with steam using phosphoric acid h3po4 catalyst coated on solid silicon. Ethaol can also be made by
fermentation of starchy material such as maize, wheat, and potatoes but this method can only be used for
manufacture of ethanol, other alcohols cannot be manufactured by this method. Alcohols can be
dehydrated in the lab to make alkenes – for example, dehydrating ethanol to make ethene using
aluminium oxide as a catalyst or acid catalysed (conc. H 2SO4 at elevated temperature). Sodium metal
reacts steadily with ethanol to give off bubbles of hydrogen gas and leaves a colourless solution of sodium
ethoxide, CH3CH2ONa. This reaction is normally used to dispose off small amounts of sodium metal
safely.
Primary alcohols can be oxidised to either aldehydes or carboxylic acids depending on the reaction
conditions. In the case of the formation of carboxylic acids, the alcohol is first oxidised to an aldehyde
which is then oxidised further to the acid, secondary alcohols can be oxidized to ketone while tertiary
alcohols cannot be oxidized. The oxidation of primary and secondary alcohols with potassium dichromate
vi is the basis of picking out tertiary alcohol from the other two because with primary and secondary
alcohols the orange colour of potassium dichromate changes to green but with tertiary alcohol there is no
colour change. To distinguish between primary and secondary alcohols we use schiff’s reagent on the
oxidation products of primary and secondary alcohols. Schiff’s reagent gives deep magenta colour with
aldehydes in cold, but with ketones in cold there is no colour change. Esters are derived from carboxylic
acids by replacement of the h in the carboxyl group (COOH) of the carboxylic acid by an alkyl group of
some kind.
Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst.
The catalyst is usually concentrated sulphuric acid; such esterification process is slow and reversible.
Other and better ways of producing esters involve reaction of an alcohol with acyl halide (RCOCl) or an
anhydride R(CO)2O. The -OH group in an alcohol can be replaced by a halogen to give haloalkane and
there are a number of methods to achieve this transformation including reaction with phosphorus III
halides PCl3, phosphorus V halides (PCl5) and sulfur dioxide chloride SO2Cl (commonly known as thionyl
chloride).

In Lecture 16 we learned that Carbonyl compounds are compounds which contain a carbon-oxygen
double bond C = O (carbonyl group), examples of these are aldehydes and ketones. In aldehydes, the
carbonyl group has a hydrogen atom attached to it together with either:

(a) -a second hydrogen atom

(b) -or, more commonly, a hydrocarbon group which might be an alkyl group or one containing a
benzene ring.

The carbon-oxygen double bond very highly polar.

 
C O

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The slightly positive carbon atom in the carbonyl group can be attacked by nucleophiles. A nucleophile is a
negatively charged ion (for example, a cyanide ion, CN-), or a slightly negatively charged part of a molecule
(for example, the lone pair on a nitrogen atom in ammonia, NH3). During the reaction, the carbon-oxygen
double bond gets broken. The net effect of all this is that the carbonyl group undergoes addition reactions,
often followed by the loss of a water molecule. Such a reaction known as addition-elimination or
condensation. An aldehyde differs from a ketone by having a hydrogen atom attached to the carbonyl group
and aldehydes are more reactive than ketones. aldehydes and ketones can both be reduced to alcohols.
Reduction of an aldehydes gives a primary alcohol while that of a ketone gives a secondary alcohol.

And finally, Lecture 17 concluded the Module by introducing Crboxylic acids as compounds which
contain a -COOH group. Caboxylic acids can be prepared from primary alcohols by a two–step oxidation
using potassium dichromate VI. Carboxylic acids can also be prepared by acid or alkaline hydrolysis of
nitriles. In the presence of water, the carboxylic acids don't dimerise. Instead, hydrogen bonds are formed
between water molecules and individual molecules of acid. The carboxylic acids with up to four carbon
atoms will mix with water in any proportion. The boiling points of carboxylic acids are much higher than
those of alcohols of comparable number of carbon atoms.

209
 Exercise
1. Explain why the reactivities of alkyl halides are in the trend shown as we change the halide: RI
>RBr >RCl >RF?

2. In the reaction of alkyl halides with nucleophiles which one is the better nucleophile -OH or
H2O?

3. What is the major structural difference between alkyl halides and aryl halides?

4. Why are aryl halides insoluble in water?

5. Write the structure of the Grignard reagent that can be prepared from chlorobenzene.
6. What disadvantage is there in preparing ester by reaction of alcohol with carboxylic acid?
7. Write a balanced equation between an acyl halide and alcohol to form ester.

8. What is the functional group in any carboxylic acid?

9. Name any naturally occurring carboxylic acid.

References
1. Klein, D. (2012) Organic Chemistry. John Wiley and Sons Inc., Hoboken, US.
2. Loudon, M.G. (2009). Organic Chemistry 5th Edition. Roberts Publishers.
3. McMurry, J. (1995). Organic Chemistry 4th Ed. Pacific Grove. Albany. Boston. Cincinnati. Detroit.
London. Madrid. Melbourne. Mexico City. New York. San Francisco. Singapore. Tokyo.
Toronto. Washington. Brooks/Cole Publishing company.
4. Maitland Jones, Jr. (2nd ed.) 2000. Organic Chemistry (Chapters 12, 13, & 24). New York. London.
W.W. Norton & Company, (Publishers).

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The Periodic Table of Elements