CHEM 111 E-Learning Material-1

EGERTON UNIVERSITY
CHEMISTRY DEPARTMENT
E-LEARNING MATERIAL
CHEM 130: GENERAL INORGANIC AND PHYSICAL CHEMISTRY
Credit Factor: 3.0 (Lectures 30 Hrs. Practicals 30 Hrs.)
STREAMS:
BSc. (HORT, AGEC, FOST, FOND, AGED, SELUM, DATM, ANHE, AGHE, ANSC,
AGRO, NARE, WIEM, AQUA, ENSC, IFORM, AGEN, WEEN, ICEN, MENT)
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Course Instructors: Mr. J. Bosire, Mr. E. Osoro, Ms. D. Nyamboki, Mr. A. Kimemia
August, 2020
________________________________________________________
Is this course for you?
This course has been designed for first year undergraduate students of
Egerton University pursuing Bachelor of Science(HORT, AGEC, FOST,
FOND, AGED, SELUM, DATM, ANHE, AGHE, ANSC, AGRO, NARE, WIEM,
AQUA, ENSC, IFORM, AGEN, WEEN, ICEN, MENT). You are expected to
complete the course in 45 hours within a period of one semester.
Introduction to the course
This course will introduce you to general concepts of inorganic and

physical chemistry, including the atomic structure, stoichiometry, the
modern periodic table, chemical bonding, kinetic theory and states of
matter, rates of reactions, chemical equilibrium, electrochemistry and
thermochemistry. We hope you will enjoy the course.
Learning Outcomes
At the end of the course, learners should be able to:
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1. To explain the atomic structure in relation to chemical reactions
2. To perform the various chemical calculations in mole concept
stoichiometry
3. To explain the union of elements in chemical bonding
4. To explain the periodic table of elements and trends
5. To explain the three states of matter
6. To calculate the Kw, Ka, Kc, Kp , Kb of solutions
7. To calculate the e.m.fs of cells
8. To determine the order of reactions
9. To determine the enthalpy changes of reactions
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TABLE OF CONTENTS
TOPIC ONE: ATOMS AND ELEMENTS..................................................6
1.1 Dalton’s atomic theory..............................................................7
1.1.1 Postulates of Dalton’s atomic theory..........................................7
1.1.2 Limitations/drawbacks of Dalton’s atomic theory.........................7
1.2 The fundamental components of atoms........................................7
1.2.1 Atomic Number (Z).................................................................8
1.2.2 Mass number (A)....................................................................8
1.2.3 Isotopes................................................................................8
1.3 Relative Atomic Mass................................................................9
1.4 Review of Atomic Structure.....................................................10
1.4.1 Rutherford’s atomic model.....................................................10
1.5 Further Reading/References...................................................13
1.6 Review Questions...................................................................13
1.7Activity....................................................................................14
TOPIC TWO: STOICHIOMETRY & CHEMICAL CALCULATIONS...........15
2.1 Avogadro’s Number & The Mole Concept.................................16
2.2 Determining the Formula of a Compound................................17
2.2.1 Percent Composition.........................................................17
2.2.2 Empirical and Molecular Formula.......................................18
2.3 Ways of Expressing Concentrations of Solutions.....................20
2.3.1 Percent Concentration;..........................................................20
2.3.2 Concentration by mass; ppm & ppb.........................................21
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2.3.3 Molarity (M).........................................................................22
2.3.4 Molality (m).........................................................................22
2.3.5 Normality.............................................................................22
2.4 Stoichiometric Calculations: Amounts of Reactants and

Products.......................................................................................25
2.4.1 Calculations involving a limiting reagent...................................26
2.4.2 Calculating the Percentage Yield..............................................28
2.7 Activity...................................................................................31
CHAPTER THREE: MODERN PERIODIC TABLE...................................32
3.1 Electronic Structure................................................................32
3.1.1 Quantum Numbers................................................................32
3.1.2 Atomic Orbitals.....................................................................33
3.2 Relationship between Quantum Numbers and atomic orbitals 34
3.3 Writing Electron Configurations..............................................34
3.3.1 Pauli Exclusion Principle.........................................................35
3.3.2 Hund’s Rule..........................................................................35
3.3.3 Aufbau Principle....................................................................36
3.4 Properties of Monatomic Ions.................................................38
3.4.1 Shielding effect.................................................................39
3.5 Evidence for Electronic Structure of atoms..............................40
3.5.1 Using Ionisation energies to predict electronic structure -evidence

of shells.......................................................................................41
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3.6 The Periodic Table...................................................................41
3.6.1 Development of the Periodic Table...........................................41
3.6.2 Modern Periodic Table.......................................................42
3.6.3 Periodic Classification of Elements...........................................44
3.6.4 Electronic configuration in relation to periodic table...................44
3.7 General Trends in Physical and Chemical Properties in Period 3,

Group I, II and VII.......................................................................45
3.7.1 Atomic Size (Atomic Radius)................................................45
3.7.2 Moving Across a Period..........................................................45
3.7.3 Moving Down a Group............................................................45
3.7.4 Cations and Anions................................................................45
3.7.5 Ionization Energy and Electron Affinity.....................................46
3.7.6 Electronegativity...................................................................48
3.10 Activity.................................................................................50
CHAPTER FOUR: CHEMICAL BONDING.............................................51
4.1 Chemical Bond........................................................................52
4.2 Lewis Symbols & Structures....................................................52
4.3 Ionic Bond..............................................................................56
4.3.1 Electrovalency......................................................................57
4.3.2 Factors Governing the Formation of Ionic Bonds........................57
4.3.3 Properties of Ionic compounds................................................58
4.4 Covalent Bond.........................................................................59
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4.4.1 Polar Covalent Bond..............................................................61
4.4.5 Intermolecular Forces in Covalent Compounds..........................62
4.6 Activity..................................................................................65
TOPIC FIVE: THE KINETIC THEORY AND STATES OF MATTER...........66
5.1 States of matter......................................................................66
5.2 Introduction to Kinetic Theory of Gases..................................67
5.2.1 Postulates of the kinetic theory of gases...................................68
5.2.2 Assumptions for the Kinetic Theory of Gases.............................68
5.2.3 How Do Ideal Gases Differ from Real Gases?............................69
5.3 The Ideal Gas Laws.................................................................69
5.3.1 Boyle’s Law..........................................................................69
5.3.2 Charles’ Law......................................................................70
5.3.3 Combined Gas Law................................................................72
5.3.4 Avogadro’s Law....................................................................73
5.3.5 The Ideal Gas Equation..........................................................73
5.4 Imperfect Gases (Real Gases).................................................75
5.5 Dalton’s Law of Partial Pressures............................................77
5.7 Further Reading/References.................................................79
5.8 Review Questions..................................................................79
5.9 Activity..................................................................................80
TOPIC SIX: RATES OF A REACTION..................................................80
6.0 Rate of Reaction......................................................................81
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6.1 Measuring Rates of Reaction...................................................81
6.2 Simple Collision Theory...........................................................83
6.3 Factors affecting the rate of a chemical reaction.....................85
6.4 Orders of Reaction and Rate Equations...................................88
6.5 The Rate equation and the Rate constant................................89
6.6 Explaining orders of reaction..................................................90
6.7 Further Reading/ References..................................................91
6.9 Activity...................................................................................93
TOPIC SEVEN: CHEMICAL EQUILIBRIUM..........................................93
7.0 Introduction to Chemical Equilibrium......................................94
7.1 Factors affecting equilibrium position.....................................94
7.2 Equilibrium Law and Equilibrium Constants............................96
7.3 Ways of expressing equilibrium..............................................97
7.4 Features of equilibrium constant.............................................98
7.5 The relationship between Kc and Kp.......................................98
7.6 Ionization of Acids and Bases.................................................99
7.7 The pH of a solution..............................................................101
7.8 Indicators.............................................................................102
7.9 Hydrolysis.............................................................................104
7.10 Solubility and solubility products........................................108
7.11 Buffer Solutions..................................................................110
7.12 Further Reading/ References..............................................114
7.13 Review Questions................................................................114
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7.14 Activity................................................................................115
TOPIC EIGHT: ELECTROCHEMISTRY...............................................116
8.0 Electrochemistry...................................................................116
8.1 Spontaneous reduction-oxidation (redox) reactions.............116
8.2 Construction of Galvanic Cells...............................................118
8.3 Electrode Potential................................................................120
8.3.1 Electromotive Force (e.m.f)..................................................121
8.3.2 Half-Cell Potential................................................................121
8.4 Cell notation..........................................................................123
TOPIC NINE: THERMOCHEMISTRY.................................................126
9.0 Thermochemistry..................................................................126
9.1 Enthalpy of a Reaction, ∆ H ....................................................126
9.1.1 Factors determining the magnitude of ∆ H ..............................127
9.2 Exothermic and Endothermic Reactions................................128
9.3 Molar Enthalpy Changes........................................................129
9.5 Further Reading/ References................................................134
9.7 Activity..................................................................................135
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TOPIC ONE: ATOMS AND ELEMENTS
Topic Introduction
John Dalton (1805) considered that all matter is composed of small

particles called atoms. He visualized the atom as a hard solid individual
particle incapable of subdivision. At the end of the nineteenth century there
accumulated enough experimental evidence to show that the atom is made
of still smaller particles. These subatomic particles are called the
fundamental particles. The number of subatomic particles now known is
very large. For us, the three most important are the proton, neutron and
electron. How these fundamental particles go to make the internal structure
of the atom, is a fascinating story. This topic explores the main events
leading to the discovery of the atomic structure.
Learning Outcomes
By the end of this topic, the student should be able to;
 Describe Dalton’s atomic theory model

 Appreciate that all forms of matter are composed of one or more
elements.
 Define the terms atomic number and atomic mass and be able to
describe their significance.
 Describe the atomic structure, how protons, electrons, and neutrons
are arranged into atoms and ions.
Topic times
 Compulsory online reading, activities, self-assessment and practice
exercises: 3 hrs
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 Optional further reading: 1.5 hrs
 Total student input: 4.5 hrs
What is chemistry?
Science of matter, the branch of natural science dealing with the

composition of substances, their properties and reactions.
What is inorganic chemistry?
Is the study of reactions and properties of all chemical compounds that do

not contain carbon-hydrogen bond (organic compounds).
1.0 Atoms and Atomic structure
An atom is the smallest unit quantity of an element that is capable of

existence, either alone or in chemical combination with other atoms of the
same or another element.
An atom is the smallest invisible particle of an element that takes part in a

chemical reaction.
Atomic structure is the study of the constituents of an atom.
1.1 Dalton’s atomic theory

Dalton is considered as the father of atomic theory of matter. He was the
pioneer scientist to provide the basic theory of the components of matter.
Dalton theorized that all matter is made up of small indivisible units called
atoms.
1.1.1 Postulates of Dalton’s atomic theory

1. All matter consists of tiny, indestructible particles called atoms.
2. The atoms of one particular element are all identical in mass, size,
shape and other properties.
3. The atoms of different elements differ in mass and other properties.
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4. A chemical reaction involves, union, disunion and rearrangement of
atoms to form molecules and compounds.
5. When atoms of different elements combine in definite numerical ratio
to form compounds or new more complex particles.
1.1.2 Limitations/drawbacks of Dalton’s atomic theory

1. An atom is not the smallest particle of an element. It contains other
sub atomic particles (electrons, neutrons and protons).
2. An atom of an element can be destroyed. It can be divided by
radioactive means.
3. Atoms of the same element may not be identical in mass since they
may exist as isotopes with different masses.
1.2 The fundamental components of atoms

Consists of three fundamental particles
Particles Mass (G) Charge (C) Charge

Electron (e-) 9.1094×10-28 -1.602×10-19 1-
Proton (p) 1.6726× 10-24 1.602×10-19 1+
Neutron (n) 1.67493× 10-24 Neutral (0) 0
 Electrons surround the atom’s nucleus (circular outer space).
 Protons are found within the atomic nuclei
 Neutrons are found within the atomic nuclei
Nucleus is the central part of an atom and is composed of protons and

neutrons and it contains most of an atom’s mass (p+n).
1.2.1 Atomic Number (Z)

Is the number of protons in the nucleus of an atom of an element (a
substance that is made entirely from one type of atom e.g. H is made from
atoms containing a single proton and electron.) and is equal to the number
of electrons in the outer shells of a neutral atom.
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Significance of atomic number
It characterizes the chemical properties of the element or atom
Helps us in knowing the position of the element in the periodic table.
Atomic Number = Number of protons = Number of electrons
1.2.2 Mass number (A)

It is the total number of neutrons and protons present in the nucleus of an
atom of an element. Except for the most common form of hydrogen, which
has one proton and no neutrons, all atomic nuclei contain both protons and
neutrons. In general, the mass number is given by:
Mass number = Number of protons + Number of neutrons
The number of neutrons in an atom is equal to the difference between the

mass number and the atomic number, or (A -Z). For example, if the mass
number of a particular boron atom is 12 and the atomic number is 5
(indicating 5 protons in thenucleus), then the number of neutrons is: 12-5 =
7.
Each nucleus species of an element is known as a nuclide. The symbol for a

nuclide is given as
X Where X is the unknown element

A
Z
A= Mass Number or Atomic mass
Z= Atomic Number
1
e.g. 1 H Hydrogen element
Na Sodium element i.e. 11 protons and 12 neutrons

23
11
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1.2.3 Isotopes
Isotopes are atoms of the same element with the same atomic number (Z)
but different mass numbers (A) e.g. hydrogen has three isotopes namely;
1
1. Hydrogen 1 H
2
2. Deuterium 1 D
3
3. Tritium 1T
11 12 13 14
Carbon has 4 isotopes namely; 6C , 6C , 6C , 6C (is radioactive and unstable)
NB-An atom of an isotope is also known as nuclide
1.3 Relative Atomic Mass

The masses in the periodic table are not mass numbers, in general. They are
relative average atomic masses. Masses are defined relative to the isotope of
carbon with a mass number of 12. This isotope is defined to have a mass of
exactly 12.0000 amu.
The relative atomic mass, or atomic weight, of an element is the weighted
average of the masses of the isotopes in the naturally occurring element
relative to the mass of an atom of the carbon-12 isotope which is taken to
be exactly 12.
In order to calculate the relative average atomic mass of an element we
need to know
1. the relative masses of the individual isotopes, and
2. the abundances of the individual isotopes, and
3. the number of isotopes.
 For an element E with the naturally occurring isotopes aE, bE, cE, and
with the respective abundances of A%, B%, C% etc,
A B C
the relative atomic mass (r.a.m.) = xa+ xb+ xc
100 100 100
Solved Example
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Naturally occurring silver is 51.84% silver-107 and 48.16% silver-109.
Calculate the relative atomic mass of silver.
r.a.m. (Ag) = (51.84/100 x 107) + (48.16/100 x 109)
= 55.469 + 52.494
= 107.96
 Given the relative atomic mass (r.a.m.) of an element and the mass of
each of its isotopes, the relative abundance of each isotope can be
calculated:
y
let = abundance of isotope 1
100
100− y
and = abundance of isotope 2
100
y 100− y
then, r.a.m = [ x mass isotope 1] + [ x mass isotope 2]
100 100
and solve for y
Copper consists of two isotopes, copper-63 and copper-65.
Its relative atomic mass is 63.62.
Find the abundance of each isotope.
Let y/100 = the abundance of copper-63
and (100 - y)/100 = the abundance of copper-65
63.62 = (y/100 x 63) + [(100 - y)/100 x 65]
63.62 = 63y/100 + 6500/100 - 65y/100
6362 = 63y + 6500 - 65y
-135 = -2y
y = 69
Other Examples
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1. Naturally occurring Nitrogen is composed of 99.633% 7 N (relative
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isotopic mass= 14.00307) and 0.367%, 7 N (isotopic mass=
15.00011). Determine its relative atomic mass.
Solution:
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( 99.633 ×14.00307 )+(0.367 ×15.00011)
RAM of N= = 14.0067
100
2. Calculate the RAM of chlorine if the Relative abundance of the two Cl
35 37
isotopes is 75.78% 17Cl and 24.22% 17Cl
75.78× 35 24.22× 37
RAM of Cl = + = 35.5
100 100
1.4 Review of Atomic Structure
The positively charged protons were discovered in 1886, the negatively

charged electrons in 1897, and the neutral neutron in 1932. The protons and
neutrons are contained in the nucleus of the atom. Almost all of the mass
(99.999%) of an atom is contained in the nucleus. Because the nucleus
contains only protons and neutrons, it is positively charged.
The electrons are arranged around the nucleus. Most of the space where the
electrons are is empty. The motion of the electrons in this region determines
the size of the atom
In a neutral atom, the number of protons in the nucleus is equal to the
number of electrons in the outer part of the atom. This means that all atoms
have no charge.
1.4.1 Rutherford’s atomic model

Ernest Rutherford carried out experiments of bombarding very thin foils of
gold and other metals with alpha radiation generated from radioactive
sources. Alpha particles are positively charged particles. He expected that
the positively charged alpha particles will be deflected/repelled back by the
positively charged nucleus. However, he found out that most of the alpha (α)
particles passed through the metal strip undeflected (without coming near
nucleus), a few of α-particles were deflected (those that come close to the
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nucleus) and some of the α –particles were scattered (those that
approached the nucleus head on).
Rutherford’s conclusions about the structure of an atom
Rutherford was later able to explain the results of the a-scattering

experiment in
terms of a new model for the atom.
1. According to Rutherford, most of the atom must be empty space. This

explains why the majority of a particles passed through the gold foil
with little or no defection.
2. The atom’s positive charges, Rutherford proposed, are all concentrated
in the nucleus, which is a dense central core within the atom.
Whenever a particle came close to a nucleus in the scattering
experiment, it experienced a large repulsive force and therefore a
large defection. Moreover, a particle traveling directly toward a
nucleus would be completely repelled and its direction would be
reversed.
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3. A greater portion of the atom is empty space surrounding the nucleus
which is occupied by electrons.
4. The α-particle which rebounds strikes directly the positively charged
centre, which is also quite massive. Hence, most of the mass of the
atom is concentrated in a tiny region known as the nucleus.
Thus according to Rutherford, an atom is spherical with electrons residing

in circular orbitals around the nucleus.
The electrons in a particular orbital will remain in position when the

attractive force balances the centrifugal force.
Limitation
By the laws of classical physics, a charged body moving in a circular path

at high speed loses energy continuously. Therefore a moving electron will
lose energy and eventually will spiral in to nucleus.
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Hence ; i) The atom is unstable, ii) the properties of the atom may not be
adequately accounted for, especially formation of spectra or claws when
heated.
Topic Summary
Chemistry;
Science of matter, the branch of natural science dealing with the

composition of substances, their properties and reactions.
Inorganic chemistry;
Is the study of reactions and properties of all chemical compounds that do

not contain carbon-hydrogen bond (organic compounds).
Atomic structure;
Small dense nucleus contains protons and neutrons.
• Protons—positive charge
• Neutrons—no charge
Electrons reside outside the nucleus in the relatively large remaining atomic
volume.
• Electrons—negative charge, small mass (11840 of proton)
Isotopes have the same atomic number but different mass numbers.
1.5 Further Reading/References
1. James E. Brady. General Chemistry. Principles and structure. - 5 th
Edition. ISBN 0-471-62131-5
2. CHEMISTRY- Matter and It’s Changes, BRADY, RUSSELL, HOLUM- 3 rd
EDITION. ISBN 0-471-18476-4
3. Raymond Chang, Brandon Cruickshank. Chemistry -. Williams College.
ISBN 0-07-25124-4 8th Edition
4. House, J. E. (2008): Inorganic Chemistry, Elsevier Inc. 2nd Ed.
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5. Kenneth, M. M. Rosemary, A. M. Henderson, W. (2002): Introduction to
Modern inorganic, Chemistry Nelson Thornes 6th Ed.
1.6 Review Questions

1. Write the atomic symbol (ZAX) for each of the isotopes described
below.
a. number of protons 27, number of neutrons 31
b. the isotope of boron with mass number 10
c. Z =12, A=23
d. atomic number 53, number of neutrons 79
e. Z 9, number of neutrons 10
f. number of protons 29, mass number 65
2. Do the proton and the neutron have exactly the same mass?
How do the masses
of the proton and neutron compare to the mass of the electron?
Which particles
make the greatest contribution to the mass of an atom? Which
particles make
the greatest contribution to the chemical properties of an atom?
3. Give an account of the experiment which led Rutherford to
conclude that every atom has a positively
charged nucleus which occupies a very small volume. What were
the drawbacks of Rutherford’s nuclear model of the atom?
4. The element rhenium (Re) has two naturally occurring
isotopes,185Re and 187Re, with an average atomic mass of
186.207 amu. Rhenium is 62.60% 187Re, and the atomic mass
of 187Re is186.956 amu. Calculate the mass of 185Re.
5. An element consists of 1.40% of an isotope with mass 203.973
amu, 24.10% of an isotope with mass 205.9745 amu, 22.10% of
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an isotope with mass 206.9759 amu, and 52.40% of an isotope
with mass 207.9766 amu. Calculate the average atomic mass
and identify the element.
1.7Activity
Students should attempt the review questions in section 1.6.
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TOPIC TWO: STOICHIOMETRY & CHEMICAL
CALCULATIONS
Course Introduction
Chemical reactions have a profound effect on our lives. The central activity
of chemistry is to understand chemical changes and the study of reactions
occupies a central place in this topic. We will examine why reactions occur
and the specific how they occur. In this chapter we will consider the
quantities of materials consumed and produced in chemical reactions. This
area of study is called chemical stoichiometry (pronounced stoy ke– om
etry). To understand chemical stoichiometry, you must first understand the
concept of relative atomic masses.
Learning Outcomes
 Describe the various units of material quantification in chemistry.

 Determine Empirical Formulae, Molecular Formulae and Percentage
Composition of substances.
 Express solutions into various units of concentration; Molarity,
Normality and Percentage concentration.
 Compute the quantities of materials in consumed and produced in a
chemical reaction
Topic times
exercises: 3 hrs
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Stoichiometry is a branch of chemistry that deals with the relative quantities
of reactants and products in chemical reactions. In a balanced chemical
reaction, the relations among quantities of reactants and products typically
form a ratio of positive integers.
The law of definite proportions states that the element ratios for a given
compound remain constant. The subscripts in a chemical formula may
therefore be used to define molar ratios between the elements in the
formula or between an element and the compound.
2.1 Avogadro’s Number & The Mole Concept

Avogadro's number and the mole are very important to the understanding of
atomic structure. The SI definition of the mole is the amount of substance
that contains as many entities as there are in exactly 12g of carbon. Thus,
the mass of 1 mole of an element is equal to its atomic mass in grams.
The Mole is like a dozen. You can have a dozen guitars, a dozen roosters, or
a dozen rocks. If you have 12 of anything then you would have what we call
a dozen. The concept of the mole is just like the concept of a dozen. You can
have a mole of anything. The number associated with a mole is Avogadro's
number. Avogadro's number 6.02 x 1023. 1 mole of anything contains 6.02 x
1023 units of that substance. Thus, the actual number of atoms that is
needed to give the relative atomic mass of an element expressed in grams is
called Avogadro's number (symbol L)
Avogadro's number = 6.02 x 1023
Thus;
Mass of Substance
Number of Moles ¿
RAM∨RMM
Example 1;
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Aluminum (Al) is a metal with a high strength-to-mass ratio and a high
resistance to corrosion; thus it is often used for structural purposes.
Compute both the number of moles of atoms and the number of atoms in a
10.0-g sample of aluminum.
Solution
The mass of 1 mole (6.022 ×1023 atoms) of aluminum is 26.98 g. The
sample we are
considering has a mass of 10.0 g. Since the mass is less than 26.98 g, this
sample contains
less than 1 mole of aluminum atoms. We can calculate the number of moles
of aluminum
atoms in 10.0 g as follows:
Example 2;
Cobalt (Co) is a metal that is added to steel to improve its resistance to

corrosion. Calculate both the number of moles in a sample of cobalt
containing 5.00 ×1020 atoms and
the mass of the sample.
Solution
Note that the sample of 5.00 ×1020 atoms of cobalt is less than 1 mole
(6.022 × 1023 atoms)
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of cobalt. What fraction of a mole it represents can be determined as
follows:
Since the mass of 1 mole of cobalt atoms is 58.93 g, the mass of 5.00×10 20
atoms can
be determined as follows:
2.2 Determining the Formula of a Compound

2.2.1 Percent Composition
The percent composition of a component in a compound is the percent of the
total mass of the compound that is due to that component
Example Percent Composition Problem
Calculate the percent composition of carbon in each of the following:
CO2
Molar mass of compound:

Mass due to carbon: 12.01 g/mol
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Percent composition of carbon:
C6H12O6
Molar mass of compound:
Mass due to carbon:
Percent composition of carbon:
2.2.2 Empirical and Molecular Formula
 Empirical Formula of a compound shows the ratio of elements present

in a compound. A formula that gives the simplest whole-number ratio
of atoms in a compound.
 Molecular Formula of a compound shows how many atoms of each
element are present in a molecule of the compound.
 The empirical formula mass of a compound refers to the sum of the
atomic masses of the elements present in the empirical formula.
 The Molecular Mass (formula mass, formula weight or molecular
weight) of a compound is a multiple of the empirical formula mass.
MM = n x empirical formula mass
 Empirical Formula can be calculated from the percentage (or percent)
composition of a compound.
Calculating Empirical Formula from Percentage Composition
1. Assume 100g of sample

2. Convert all percentages to a mass in grams, eg, 21% = 21g, 9% = 9g
3. Find the relative atomic mass (r.a.m) of each element present using
the Periodic Table
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4. Calculate the moles of each element present: n = mass ÷ r.a.m
5. Divide the moles of each element by the smallest of these to get a
mole ratio
6. If the numbers in the mole ratio are all whole numbers (integers)
convert this to an empirical formula
7. If the numbers in the mole ratio are NOT whole numbers, you will
need to further manipulate these until the mole ratio is a ratio of whole
numbers (integers)
Example 1
A compound is found to contain 47.25% copper and 52.75% chlorine.

Find the empirical formula for this compound.
element Cu Cl
mass in grams 47.25 52.75
r.a.m 63.6 63.6
moles = mass ÷ 47.25 ÷ 63.6 = 52.75 ÷ 35.5 =
r.a.m 0.74 1.49
divide throughout 0.74 ÷ 0.74 = 1 1.49 ÷ 0.74 =
by lowest number 2.01 = 2
Empirical formula for this compound is CuCl2
Example 2
A compound with a molecular mass of 34.0g/mol is known to contain 5.88%

hydrogen and 94.12% oxygen.
Find the molecular formula for this compound.
First, find the empirical formula of the compound.
Element H O
mass in grams 5.88 94.12
r.a.m 1.0 16.0
18
moles = mass ÷ r.a.m 5.88 ÷ 1.0 = 5.88 94.12 ÷ 16.0 =
5.88
divide throughout by lowest 5.88 ÷ 5.88 = 1 5.88 ÷ 5.88 =
number
Empirical formula is HO
Calculate the empirical formula mass: 1.0 + 16.0 = 17.0 g/mol
Molecular Mass = n x empirical formula mass
34.0 = n x 17.0
n = 34.0 ÷ 17.0 = 2
Molecular Formula is 2 x (HO) which is H2O2
2.3 Ways of Expressing Concentrations of Solutions

The Concentration of a Solution is defined as the relative amount of solute
present in a solution. In this subtopic, we shall delve into the various ways
of expressing the concentration of a solute in a solution. They include;
2.3.1 Percent Concentration;

 Mass percent (w/w%)- “It represents mass of a component
present in 100 g of
solution”
 Volume percentage (%v/v)-“It represents volume of a

component in 100 mL of solution”
19
 Mass by volume percentage (%w/v)- “It represents mass of
solute in grams present in 100 mL of solution”
Example:
Consider 5 g sugar dissolved in 20 g of water. What is the w/w%

concentration of sugar in this solution?
5 g of sugar
×100=20 w /w %
25 g of water
2.3.2 Concentration by mass; ppm & ppb

Parts per million (ppm) and parts per billion (ppb) are examples of
expressing concentrations by mass. These units turn out to be convenient
when the solute concentrations are very small (almost trace amounts).
Ppm is defined as the parts of a component per million parts (106) of the
solution. It is widely used when a solute is present in trace quantities
Example;
For example, suppose a 155.3 g sample of pond water is found to have
1.7x10^-4 g of phosphates. What is the concentration of phosphates in
ppm?
20
A similar procedure would be followed to calculate ppb. In the above
example the pond water would be 1,100 ppb.
2.3.3 Molarity (M)

Molarity is the number of moles of solute dissolved in one liter of solution.
The units, therefore are moles per liter, specifically it's moles of solute
per liter of solution.
moles of solute
Molarity =
liter of solution
Units of Molarity are mol/L also represented by ‘M’ or ‘Molar’.
“Density of a solution is mass of the solution per unit volume”
2.3.4 Molality (m)

Molality represents moles of solute present per kg of solvent.
Units of molality are mol/kg which is also represented by ‘m’ or ‘molal’.
2.3.5 Normality
It represents no. of equivalents of solute present in 1 L of solution.
21
The normality of a solution is simply a multiple of the molarity of the
solution. Generally, the normality of a solution is just one, two or three
times the molarity.
Whether the multiplying factor is one, two or three depends on the formula
of the chemical and what it is being compared to.
Example;
22
Also,
N/B: ppm = 1g/m3 = 1mg/L = 1μg/mL
1ppm = 1mg/kg = 1μg/g
More examples;
Converting weight/volume (w/v) concentrations to ppm
1. A solution has a concentration of 1.25g/L.

What is its concentration in ppm?
1. Convert the mass in grams to a mass in milligrams:

1.25g = 1.25 x 1000mg = 1250mg
2. Re-write the concentration in mg/L = 1250mg/L = 1250ppm
2. A solution has a concentration of 0.5mg/mL.

1. Convert the volume to litres:

volume = 1mL = 1mL ÷ 1000mL/L = 0.001L
2. Re-write the concentration in mg/L = 0.5mg/0.001L = 500mg/L =
500ppm
23
Converting weight/weight (w/w) concentrations to ppm
1. A solution has a concentration of 0.033g/kg.

1. Convert mass in grams to mass in milligrams:

0.033g = 0.033g x 1000mg/g = 33mg
2. Re-write the concentration in mg/kg = 33mg/kg = 33ppm
2. A solution has a concentration of 2250μg/kg.

1. Convert mass in μg to mass in mg:

2250μg = 2250μg ÷ 1000μg/mg = 2.25mg
2. Re-write the concentration in mg/kg = 2.25mg/kg = 2.25ppm
Parts Per Million (ppm) Concentration Calculations
1. 150mL of an aqueous sodium chloride solution contains 0.0045g NaCl.

Calculate the concentration of NaCl in parts per million (ppm).
1. ppm = mass solute (mg) ÷ volume solution (L)

2. mass NaCl = 0.0045g = 0.0045 x 1000mg = 4.5mg
volume solution = 150mL = 150 ÷ 1000 = 0.150L
3. concentration of NaCl = 4.5mg ÷ 0.150L = 30mg/L = 30ppm
2. What mass in milligrams of potassium nitrate is present in 0.25kg of a

500ppm KNO3(aq)?
1. ppm = mass solute (mg) ÷ mass solution (kg)

2. Re-arrange this equation to find the mass of solute:
mass solute (mg) = ppm x mass solution (kg)
24
3. Substitute in the values:
mass KNO3 = 500ppm x 0.25kg = 125mg
3. A student is provided with 500mL of 600ppm solution of sucrose.

What volume of this solution in millilitres contains 0.15g of sucrose?
1. ppm = mass solute (mg) ÷ volume solution (L)

2. Re-arrange this equation to find volume of solution:
volume solution (L) = mass solute (mg) ÷ ppm
3. Substitute in the values:
volume solution (L) = (0.15g x 1000mg/g) ÷ 600 = 0.25L
4. Convert litres to millilitres: volume solution = 0.25L x 1000mL/L =
250mL
2.4 Stoichiometric Calculations: Amounts of Reactants and Products

To perform stoichiometric calculations, the following steps are necessary;
Example;
Solid lithium hydroxide is used in space vehicles to remove exhaled carbon

dioxide from
the living environment by forming solid lithium carbonate and liquid water.
What mass
of gaseous carbon dioxide can be absorbed by 1.00 kg of lithium hydroxide?
25
2.4.1 Calculations involving a limiting reagent
A limiting reactant (or limiting reagent) is the reactant that is consumed
first in a chemical reaction and that therefore limits the amounts of products
that can be formed. In any stoichiometry calculation involving a chemical
reaction, it is essential to determine which reactant is limiting so as to
calculate correctly the amounts of products that will be formed.
Example;
Nitrogen gas can be prepared by passing gaseous ammonia over solid

copper (II) oxide at high temperatures. The other products of the reaction
are solid copper and water vapor. If a sample containing 18.1 g of NH3 is
reacted with 90.4 g of CuO, which is the limiting reactant? How many grams
of N2 will be formed?
26
The amount of a product formed when the limiting reactant is completely
consumed
is called the theoretical yield of that product. In the above example, 10.6
grams of nitrogen represents the theoretical yield. This is the maximum
amount of nitrogen that can be produced from the quantities of reactants
27
used. Actually, the amount of product predicted by the theoretical yield is
seldom obtained because of side reactions (other reactions that involve one
or more of the reactants or products) and other complications. The actual
yield of product is often given as a percentage of the theoretical yield. This is
called the percent yield:
For example, if the reaction considered above actually gave 6.63 grams of
nitrogen instead of the predicted 10.6 grams, the percent yield of nitrogen
would be
2.4.2 Calculating the Percentage Yield

Consider the example of methanol formation;
Methanol (CH3OH), also called methyl alcohol, is the simplest alcohol. It is

used as a fuel in race cars and is a potential replacement for gasoline.
Methanol can be manufactured by combination of gaseous carbon monoxide
and hydrogen. Suppose 68.5 kg CO(g) is re acted with 8.60 kg H2(g).
Calculate the theoretical yield of methanol. If 3.57×104 g CH3OH is actually
produced, what is the percent yield of methanol?
28
Topic Summary
Stoichiometry
Deals with the amounts of substances consumed and/or produced in a
chemical reaction.
We count atoms by measuring the mass of the sample.
To relate mass and the number of atoms, the average atomic mass is
required.
29
Mole
12
The amount of carbon atoms in exactly 12 g of pure C
6.022 ×1023 units of a substance
The mass of one mole of an element the atomic mass in grams
Molar mass
Mass (g) of one mole of a compound or element
Obtained for a compound by finding the sum of the average masses of
its constituent
atoms
Empirical formula
The simplest whole-number ratio of the various types of atoms in a
compound
Can be obtained from the mass percent of elements in a compound
Molecular formula
For molecular substances:
• The formula of the constituent molecules
• Always an integer multiple of the empirical formula
For ionic substances:
• The same as the empirical formula
Chemical reactions
Reactants are turned into products.
Atoms are neither created nor destroyed.
All of the atoms present in the reactants must also be present in the
products.
Characteristics of a chemical equation
Represents a chemical reaction
Reactants on the left side of the arrow, products on the right side
When balanced, gives the relative numbers of reactant and product
molecules or ions
30
Stoichiometry calculations
Amounts of reactants consumed and products formed can be
determined from the
balanced chemical equation.
The limiting reactant is the one consumed first, thus limiting the
amount of product that can form.
Yield
The theoretical yield is the maximum amount that can be produced
from a given
amount of the limiting reactant.
The actual yield, the amount of product actually obtained, is always
less than the
theoretical yield


1. You know that chemical A reacts with chemical B. You react 10.0 g A with
10.0 g B. What information do you need to determine the amount of product
that will be produced? Explain
2. Can the subscripts in a chemical formula be fractions? Explain. Can the

coefficients in a balanced chemical equation be fractions? Explain. Changing
31
the subscripts of chemicals can balance the equations mathematically. Why
is this unacceptable?
3. What is the difference between the molar mass and the empirical formula
mass of a compound? When these are masses the same and when are they
different? When different, how is the molar mass related to the empirical
formula mass?
4. The molecular formula of acetylsalicylic acid (aspirin), one of the most

commonly used pain relievers, is C9H8O4.
a. Calculate the molar mass of aspirin.
b. A typical aspirin tablet contains 500 mg of C9H8O4. What amount

(moles) of C9H8O4 molecules and what number of molecules of
acetylsalicylic acid are in a 500 mg tablet?
5. Ascorbic acid, or vitamin C (C6H8O6), is an essential vitamin. It cannot be

stored by the body and must be present in the diet. What is the molar mass
of ascorbic acid? Vitamin C tablets are taken as a dietary supplement. If a
typical tablet contains 500.0 mg of vitamin C, what amount (moles) and
what number of molecules of vitamin C does it contain?
6. Why is the actual yield of a reaction often less than the theoretical yield?
7. Acrylonitrile (C3H3N) is the starting material for many synthetic carpets

and fabrics. It is produced by the following reaction
If 15.0 g C3H6, 10.0 g O2, and 5.00 g NH3 are reacted, what mass of
acrylonitrile can be produced, assuming 100% yield?
2.7 Activity
Students to attempt and discuss the review questions in section 2.6
32
CHAPTER THREE: MODERN PERIODIC TABLE
Topic Introduction
In the modern periodic table, the elements are placed in order of increasing
atomic number (the number of protons). There have been numerous designs
of the table over the years, but the two most common are the long form and
the short form. In this topic, we shall explore both the short and long forms
of the periodic table, describe the electronic configuration and general trends
of the elements.
Learning Outcomes
By the end of this topic, students will be able to:
 Understand the grouping of elements in the periodic table.

 Do electronic configuration and relate with the configuration with
grouping of elements in the periodic table.
 Identify trends in the Periodic Table.
Topic times
exercises: 3 hrs
3.1 Electronic Structure
3.1.1 Quantum Numbers

Four quantum numbers are required to describe the distribution of electrons
in an atom.
33
(i) The principal quantum number (n) describes the size of the orbital.
Orbitals for which n = 2 are larger than those for which n = 1, for example.
Because they have opposite electrical charges, electrons are attracted to the
nucleus of the atom. Energy must therefore be absorbed to excite an
electron from an orbital in which the electron is close to the nucleus (n = 1)
into an orbital in which it is further from the nucleus (n = 2). The principal
quantum number therefore indirectly describes the energy of an orbital.
(ii) The angular quantum number (l) describes the shape of the orbital.
Orbitals have shapes that are best described as spherical (l = 0), polar (l =
1), or cloverleaf (l = 2). They can even take on more complex shapes as the
value of the angular quantum number becomes larger.
Each value of n has multiple values of ℓ ranging in values from 0 to (n-
1).This quantum number determines the 'shape' of the electron cloud. In
chemistry, there are names for each values of ℓ.
L 0 1 2 3 4 5
Name of S P D F g H
orbital
(iii) Magnetic Quantum Number (ml)

This number determines the orbital's orientation in space. This relationship
shows for every value of ℓ, a corresponding set of values of ml ranging from
-ℓ to ℓ is found.. For example, p orbitals correspond to ℓ=1, can have m
values of -1,0,1.
(iv) Spin quantum number,(ms). There are only two values for s, +½ and
-½. These are also referred to as 'spin up' and 'spin down'. This number is
used to explain behavior of individual electrons as if they were spinning in a
clockwise or counterclockwise.
34
3.1.2 Atomic Orbitals
This is a region or space in which there is a high probability of finding an
electron. Orbitals differ from each other in shape and orientation
(i) The s-orbital– sphere shaped and can accommodate 2
electrons. Starts with n=1
(ii) The P-orbital- dumbbell shaped and can accommodate 6

electrons. Starts with n=2
Higher Energy orbitals
In addition to s and p orbitals, there are two other sets of orbitals which
become available for electrons to inhabit at higher energy levels. At the third
level, there is a set of five d orbitals (with complicated shapes and names)
as well as the 3s and 3p orbitals (3px, 3py, 3pz). At the third level there are a
total of nine orbitals altogether.
At the fourth level, as well the 4s and 4p and 4d orbitals there are an
additional seven f orbitals - 16 orbitals in all. s, p, d and f orbitals are
then available at all higher energy levels as well.
For the moment, you need to be aware that there are sets of five d
orbitals at levels from the third level upwards, but you probably won't be
expected to draw them or name them. Apart from a passing reference,
you won't come across f orbitals at all.
3.2 Relationship between Quantum Numbers and atomic orbitals
n L ml Number Orbit Number

of al of
35
Nam electron
orbitals e s
1 0 0 1 1s 2
2 0 0 1 2s 2
1 -1, 0, +1 3 2p 6
3 0 0 1 3s 2
1 -1, 0, +1 3 3p 6
2 -2, -1, 0, +1, +2 5 3d 10
4 0 0 1 4s 2
1 -1, 0, +1 3 4p 6
2 -2, -1, 0, +1, +2 5 4d 10
-3, -2, -1, 0, +1,
3 7 4f 14
+2, +3
The four quantum numbers n, l, ml, and ms enable us to label
completely an electron in any orbital in any atom. e.g the four
quantum numbers for an electron in a 3p orbital it means that n=3,
1 −1
l=1 , ml= -1, 0, 1 and ms= ∨ , therefore there are 6 possible
2 2
1 1 1
ways of to designate the electron i.e (3,1,-1, ) , (3,1,0, ), (3,1,1,
2 2 2
−1 −1 −1
), (3,1,-1, ), (3,1,0, ), (3,1,1, )
2 2 2
3.3 Writing Electron Configurations

The distribution of electrons among the orbitals of an atom is called the
electron configuration.
Orbitals can be represented as boxes with the electrons in them shown as
arrows. Often an up-arrow and a down-arrow are used to show that the
electrons are in some way different.
36
A 1s orbital holding 2 electrons would be drawn as shown on the right, but it
can be written even more quickly as 1s 2. This is read as "one s two" - not as
"one s squared".
You mustn't confuse the two numbers in this notation:
3.3.1 Pauli Exclusion Principle
No two electrons in the same atom can have the same set of four Quantum
Numbers. If two electrons have the same n, l, and ml values (i.e the two
electrons are in the same orbital), then they must have different m s
values.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.
When we draw electrons, we use up and down arrows. So, if an electron is

paired up in a box, one arrow is up and the second must be down.
3.3.2 Hund’s Rule

When filling sublevels other than s, electrons are placed in individual orbitals
before they are paired up.
Electrons fill like people do on a bus. You would never sit right next to
someone you did not know if there are free seats available, unless of course
all the seats are taken then you must pair up.
So when working with the p sublevel, electrons fill like this....up, up,
up...down, down, down...take a look
Ato orbital box diagram
37
m
B
1s 2s 2p
C
1s 2s 2p
N
1s 2s 2p
O
1s 2s 2p
F
1s 2s 2p
Cl
1s 2s 2p 3s 3p
Mn
1s 2s 2p 3s 3p 4s
3d
3.3.3 Aufbau Principle

The electrons are filled in according to a scheme known as the Aufbau
principle ("building-up"), which corresponds (for the most part) to
increasing energy of the subshells:
The Aufbau principle states that electrons must fill lowest energy shells first.
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f
It is not necessary to memorize this listing, because the order in which the
electrons are filled in can be read from the periodic table in the following
fashion:
38
In electron configurations, write in the orbitals that are occupied by
electrons, followed by a superscript to indicate how many electrons are in
the set of orbitals (e.g., H 1s1)
Another way to indicate the placement of electrons is an orbital diagram,

in which each orbital is represented by a square (or circle), and the electrons
as arrows pointing up or down (indicating the electron spin). When electrons
are placed in a set of orbitals of equal energy, they are spread out as much
as possible to give as few paired electrons as possible (Hund's rule).
Following the model, electrons fill the 1s orbital with two electrons, then the
2s with two electrons, then the 2p with six electrons, then the 3s with two
electrons, etc.
Orbitals are no filled in numerical order i.e
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f
The 4s is filled before 3d because it is lower in energy. The effect is
explained by assuming the principal energy levels get closer together as
39
they get further from the nucleus. As a results the highest energy orbitals in
one principal level may be above the lowest orbital in the next
There are some exceptions to the Aufbau Principle. This occurs mainly with
electrons in the d orbital where extra stability is obtained from a half filled or
fully filled d orbital. Therefore, if there are 4 electrons or 9 electrons in the d
orbital, it will move one electron from the s orbital below it to fill the extra
space. e.g in the case of Chromium and copper.
3.4 Properties of Monatomic Ions

The electrons in the outermost shell (the ones with the highest value of n)
are the most energetic, and are the ones which are exposed to other atoms.
This shell is known as the valence shell. The inner, core electrons (inner
shell) do not usually play a role in chemical bonding.
Elements with similar properties generally have similar outer shell
configurations. For instance, we already know that the alkali metals (Group
I) always form ions with a +1 charge; the "extra" s1 electron is the one
that's lost:
IA Li 1s22s1 Li+ 1s2
Na 1s22s22p63s1 Na+ 1s22s22p6
K 1s22s22p63s23p64s1 K+ 1s22s22p63s23p6
40
The next shell down is now the outermost shell, which is now full — meaning
there is very little tendency to gain or lose more electrons. The ion's electron
configuration is the same as the nearest noble gas — the ion is said to be
isoelectronic with the nearest noble gas. Atoms "prefer" to have a filled
outermost shell because this is more electronically stable.
 The Group IIA and IIIA metals also tend to lose all of their valence
electrons to form cations.
IIA Be 1s22s2 Be2+ 1s2
Mg 1s22s22p63s2 Mg2+ 1s22s22p6
IIIA Al 1s22s22p63s23p1 Al3+ 1s22s22p6
 The Group VIII noble gases already possess a full outer shell, so they
have no tendency to form ions.
VIIIA Ne 1s22s22p6
Ar 1s22s22p63s23p6
 Transition metals (B-group) usually form +2 charges from losing the
valence s electrons, but can also lose electrons from the highest d
level to form other charges.
B-group Fe 1s22s22p63s23p63d64s2 Fe2+ 1s22s22p63s23p63d6
Fe3+ 1s22s22p63s23p63d5
3.4.1 Shielding effect

The shielding effect, approximated by the effective nuclear charge, is due to
inner electrons shielding valence electrons from the nucleus.
 The shielding effect describes the balance between the pull of the
protons on valence electrons and the repulsion forces from inner
electrons.
 The shielding effect explains why valence-shell electrons are more
easily removed from the atom. The effect also explains atomic size.
41
The more shielding, the further the valence shell can spread out and
the bigger atoms will be.
3.4.2 Penetration
An electron in an s orbital has a finite, albeit very small, probability of
being located quite close to the nucleus. An electron in a p or d orbital on
the other hand has a node (i.e., a region where there cannot be any electron
density) at the nucleus. Comparing orbitals within the same shell, we say
that the s orbital is more penetrating than the p or d orbitals, meaning that
an electron in an s orbital has a greater chance of being located close to the
nucleus than an electron in a p or d orbital. For this reason, electrons in an s
orbital have a greater shielding power than electrons in a p or d orbital of
that same shell. Also, because they are highly penetrating, electrons in s
orbitals are less effectively shielded by electrons in other orbitals. For
example, consider an atom of carbon whose electron configuration is
1s22s22p2. The two electrons in the 1s orbital of C will do a better job of
shielding the two electrons in the 2p orbitals than they will of shielding the
two electrons in the 2s orbital. This means that for electrons in a particular
shell, Zeff will be greater for s electrons than for p electrons. Similarly, Zeff is
greater for p electrons than for d electrons. As a result, within a given shell
of an atom, the s subshell is lower in energy than the p subshell which is in
turn lower in energy than the d subshell.
3.5 Evidence for Electronic Structure of atoms

Scientists assume that electrons in an atom can exist only at certain energy
levels. Under normal conditions, the electrons in an atom or ion fill the
lowest energy levels first. When sufficient energy is supplied to the atom, it
is possible to promote (excite) an electron from lower energy level to higher
energy level. The electron is unstable in the higher energy level, so it will
emit the excess energy as radiation and drop back to the lower energy level.
42
The energy difference between the lower and higher energy level have fixed
values because the energy levels are fixed. Therefore the radiation emitted
can have only fixed frequencies (certain specific colours).
The electronic energy levels are numbered (n=1, n=2, n=3, etc). These
numbers are the principal quantum numbers.
The figure below show the energy levels and the electron transitions
which produce lines in the visible regions of the atomic hydrogen
spectrum
In the visible region four distinct colours are seen, each represents
electrons falling to the second energy level from higher energy levels.
The lines in the specrum become progressively closer to each other i.e
they converge as the frequency or energy of the lines increase. This is
because the energy levels in an atom also get closer hence the relative
energy given out when an electron falls from say n=4 to n=2 is less than
when it falls from n=3 to n=2
3.5.1 Using Ionisation energies to predict electronic structure -

evidence of shells
If sufficient energy is given to an atom, it is possible to excite an electron
just beyond the highest energy level. In this case an electron will escape
and the atom becomes an ion. Ionisation takes place. Ionisation energy is
43
the energy required to remove one electron from an atom in gaseous
state.
If an atom with several electrons is provided with sufficient energy it will
lose one electron. Additional supply of energy will result in removal of
the 2nd electron, then a third, then a fourth and so on. A succession of
ionization is therefore possible, each of which has its associated ionization
energy. Successive ionization energies of an element are obtained from
spectroscopic experiments.
Example: Successive ionization energies of beryllium
Ionisation energy kJ/mol
First second third
fourth
900 1758 14905
21060
The values suggest that beryllium has two electrons which are relatively
easy to remove and two electrons which are difficult to remove. Chemists
deduced that the Beryllium atom has two electrons in a lower energy
level (n=1) and therefore difficult to remove, and two other electrons in a
higher energy level (n=2) and therefore easy to remove.
3.6 The Periodic Table
3.6.1 Development of the Periodic Table
Between 1817-1829, Johann Dobereiner began to group elements with

similar properties into groups of three or triads. This began in 1817 when
he noticed that the atomic weights of strontium, Sr, was halfway
between the weights of calcium and barium. These elements possessed
similar chemical properties. By 1829, he had discovered the halogen triad
made up of chlorine, bromine, and iodine and an alkali metal triad of
lithium, sodium and potassium. He postulated that nature contained
44
triads of elements in which the middle element had properties that were
an average of the other two elements. Later, other scientists found other
triads and recognized that elements could be grouped into set large than
three. The poor accuracy of measurements such as that of atomic
weights hindered grouping more elements.
In 1862, A.E.Beguyer de Chancourtois was the first person to make

use of atomic weights to reveal that the elements were arranged
according to their atomic weights with similar elements occurring at
regular intervals. He drew the elements as a continuous spiral around a
cylinder divided into 16 parts. A list of elements was wrapped around a
cylinder so that several sets of similar elements lined up, creating the first
geometric representation of the periodic law
In 1863, John Newlands, an English chemist, proposed the Law of

Octaves which stated that elements repeated their chemical properties
every eighth element.
The musical analogy was ridiculed at the time, but was found to be
insightful after the work of Mendeleev and Meyer were published.
The Fathers of the Periodic Table
Lothar Meyer and Dmitri Ivanovich Mendeleev independently

produced remarkably similar versions of the periodic table of elements at
the essentially the same time.
Meyer's 1864 textbook included a abbreviated version of a periodic table

used to classify about half of the known elements. In 1868, Meyer
constructed an extended table which he gave to a colleague for
evaluation. This table unfortunately was not published until 1870, a year
after Mendeleev's table was published.
45
Mendeleev periodic table appeared in his work "On the Relationship of
the Properties of the Elements to their Atomic Weights" in 1869.
Mendeleev placed many elements out of order based on their accepted
atomic weights at the time.
Mendeleev predicted the existence and properties of unknown elements

which he called eka-aluminum, eka-boron, and eka-silicon. The elements
gallium, scandium and germanium were found later to fit his predictions
quite well.
3.6.2 Modern Periodic Table
Glenn Seaborg discovered the transuranium elements, atomic numbers 94

to 102. The completion of the actinide series allow Seaborg to redesign the
periodic table into it current form. Both the lanthanide and actinide series of
elements were placed under the rest of the periodic table. These elements
technically should be placed between the alkaline earth metals and the
transition metals, however, since this would make the periodic table too
wide, they were placed below the rest of the elements.
Dr. Seaborg and his colleagues are also responsible for the identification of
more than 100 isotopes of elements.
Our modern day periodic table is expanded beyond Mendeleev's initial 63
elements. Most of the current periodic tables include 108 or 109 elements.
It is also important to notice how the modern periodic table is arranged.
Although we have retained the format of rows and columns, which reflects a
natural order, the rows of today's tables show elements in the order of
Mendeleev's columns. In other words the elements of what we now call a
"period" were listed vertically by Mendeleev. Chemical "groups" are now
shown vertically in contrast to their horizontal format in Mendeleev's table.
Note also that Mendeleev's 1871 arrangement was related to the atomic
46
ratios in which elements formed oxides, binary compounds with oxygen;
whereas today's periodic tables are arranged by increasing atomic numbers,
that is, the number of protons a particular element contains.
Groups
The modern periodic table of the elements contains 18 groups, or vertical
columns. Elements in a group have similar chemical and physical properties
because they have the same number of outer electrons. Elements in a group
are like members of a family--each is different, but all are related by
common characteristics. Notice that each group is titled with Roman
numerals and the letters A and B. Scientists in the United States and Europe
now use different titles to refer to the same groups. To avoid confusion, the
Roman numerals and letters designating groups will eventually be replaced
by the numerals from one to eighteen.
Periods
Each of the table's horizontal rows is called a period. Along a period, a
gradual change in chemical properties occurs from one element to another.
For example, metallic properties decrease and nonmetallic properties
increase as you go from left to right across a period. Changes in the
properties occur because the number of protons and electrons increases
from left to right across a period or row. The increase in number of electrons
is important because the outer electrons determine the element's chemical
properties. The periodic table consists of seven periods. The periods vary in
length. The first period is very short and contains only 2 elements, hydrogen
and helium. The next two periods contain eight elements each. Periods four
and five each have 18 elements. The sixth period has 32 elements.
3.6.3 Periodic Classification of Elements

The representative elements (main group elements) are the elements in
Groups 1A through 7A, all of which have incompletely filled s or p subshells
of the highest principal quantum number. With the exception of helium, the
47
noble gases (the group 8A elements ) all have a completely filled p subshell.
The Transition elements are the elements in group 1B and 3B through 8B,
which have incompletely filled d subshells or readily produce cations with
incompletely filled d subshells. (these metals are sometimes referred to as
d-block elements.) The group 2B elements are are Zn, Cd and Hg, which are
neither main group elements nor transition metals. The Lanthanides and
actinides are sometimes called f-block elements because they have
incompletely filled f subshells.
3.6.4 Electronic configuration in relation to periodic table

A clear pattern emerges when we examine the electron configuration of the
elements in a particular group. The electron configurations for group 1A
(alkali metals) have similar outer electron configuration, each has a noble
core and an ns1 configuration of the outer electron. Similarly the group 2A
(alkaline earth metals) have a noble core and an ns2 configuration of the
outer electron. The outer electrons of an atom are called valence electrons
and are those which participate in chemical bonding. Having the same
number of valence electrons accounts for similarities in chemical behavior
among the elements within each group. These observation holds true also
for group 7A (halogens), which have outer electron configuration ns 2np5 and
exhibit very similar properties. However care must be taken when predicting
properties of group 3A through 6A. e.g in gp 4A all have the same outer
electron configuration ns2np4 but there is much variation in chemical
properties among these elements: carbon is a non-metal, silicon and
germanium are metalloids and tin and lead are metals.
48
3.7 General Trends in Physical and Chemical Properties in Period 3,
Group I, II and VII
3.7.1 Atomic Size (Atomic Radius)
The atomic size of an atom, also called the atomic radius, refers to the
distance between an atom's nucleus and its valence electrons. Remember,
the closer an electron is to the nucleus, the lower its energy and the more
tightly it is held.
3.7.2 Moving Across a Period

Moving from left to right across a period, the atomic radius decreases. The
nucleus of the atom gains protons moving from left to right, increasing the
positive charge of the nucleus and increasing the attractive force of the
nucleus upon the electrons. True, electrons are also added as the elements
move from left to right across a period, but these electrons reside in the
same energy shell and do not offer increased shielding.
3.7.3 Moving Down a Group

The atomic radius increases moving down a group. Once again protons are
added moving down a group, but so are new energy shells of electrons. The
new energy shells provide shielding, allowing the valence electrons to
experience only a minimal amount of the protons' positive charge.
3.7.4 Cations and Anions

Cations and anions do not actually represent a periodic trend in terms of
atomic radius, but they do affect atomic radius, and so we will discuss them
here.
A cation is positively charged, meaning that it is an atom that has lost an
electron or electrons. The positive charge of the nucleus is thus distributed
over a smaller number of electrons and electron-electron repulsion is
decreased, meaning that the electrons are held more tightly and the atomic
radius is smaller than in the normal neutral atom. Anions, conversely, are
49
negatively charged ions: atoms that have gained electrons. In anions,
electron-electron repulsion increases and the positive charge of the nucleus
is distributed over a large number of electrons. Anions have a greater atomic
radius than the neutral atom from which they derive.
3.7.5 Ionization Energy and Electron Affinity

The process of gaining or losing an electron requires energy. There are two
common ways to measure this energy change: ionization energy and
electron affinity.
Ionization Energy
The ionization energy is the energy it takes to fully remove an electron from
the atom. When several electrons are removed from an atom, the energy
that it takes to remove the first electron is called the first ionization energy,
the energy it takes to remove the second electron is the second ionization
energy, and so on. In general, the second ionization energy is greater than
first ionization energy. This is because the first electron removed feels the
effect of shielding by the second electron and is therefore less strongly
attracted to the nucleus. If a particular ionization energy follows a previous
electron loss that emptied a subshell, the next ionization energy will take a
rather large leap, rather than follow its normal gently increasing trend. This
fact helps to show that just as electrons are more stable when they have a
50
full valence shell, they are also relatively more stable when they at least
have a full subshell.
Ionization Energy Across a Period
Ionization energy predictably increases moving across the periodic table
from left to right. Just as we described in the case of atomic size, moving
from left to right, the number of protons increases. The electrons also
increase in number, but without adding new shells or shielding. From left to
right, the electrons therefore become more tightly held meaning it takes
more energy to pry them loose. This fact gives a physical basis to the octet
rule, which states that elements with few valence electrons (those on the left
of the periodic table) readily give those electrons up in order to attain a full
octet within their inner shells, while those with many valence electrons tend
to gain electrons. The electrons on the left tend to lose electrons since their
ionization energy is so low (it takes such little energy to remove an electron)
while those on the right tend to gain electrons since their nucleus has a
powerful positive force and their ionization energy is high. Note that
ionization energy does show a sensitivity to the filling of subshells; in
moving from group 12 to group 13 for example, after the d shell has been
filled, ionization energy actually drops. In general, though, the trend is of
increasing ionziation energy from left to right. Ionization Energy Down a
Group
Ionization energy decreases moving down a group for the same reason
atomic size increases: electrons add new shells creating extra shielding that
supersedes the addition of protons. The atomic radius increases, as does the
energy of the valence electrons. This means it takes less energy to remove
an electron, which is what ionization energy measures.
Electron Affinity
An atom's electron affinity is the energy change in an atom when that atom
gains an electron. The sign of the electron affinity can be confusing. When
51
an atom gains an electron and becomes more stable, its potential energy
decreases: upon gaining an electron the atom gives off energy and the
electron affinity is negative. When an atom becomes less stable upon
gaining an electron, its potential energy increases, which implies that the
atom gains energy as it acquires the electron. In such a case, the atom's
electron affinity is positive. An atom with a negative electron affinity is far
more likely to gain electrons.
Electron Affinities Across a Period
Electron affinities becoming increasingly negative from left to right. Just as
in ionization energy, this trend conforms to and helps explain the octet rule.
The octet rule states that atoms with close to full valence shells will tend to
gain electrons. Such atoms are located on the right of the periodic table and
have very negative electron affinities, meaning they give off a great deal of
energy upon gaining an electron and become more stable. Be careful,
though: the nobel gases, located in the extreme right hand column of the
periodic table do not conform to this trend. Noble gases have full valence
shells, are very stable, and do not want to add more electrons: noble gas
electron affinities are positive. Similarly, atoms with full subshells also have
more positive electron affinities (are less attractive of electrons) than the
elements around them.
Electron Affinities Down a Group
Electron affinities change little moving down a group, though they do
generally become slightly more positive (less attractive toward electrons).
The biggest exception to this rule are the third period elements, which often
have more negative electron affinities than the corresponding elements in
the second period. For this reason, Chlorine, Cl, (group VIIa and period 3)
has the most negative electron affinity.
52
3.7.6 Electronegativity
Electronegativity refers to the ability of an atom to attract the electrons of
another atom to it when those two atoms are associated through a bond.
Electronegativity is based on an atom's ionization energy and electron
affinity. For that reason, electronegativity follows similar trends as its two
constituent measures.
Electronegativity generally increases moving across a period and decreases
moving down a group. Flourine (F), in group VIIa and period 2, is the most
powerfully electronegative of the elements. Electronegativity plays a very
large role in the processes of Chemical Bonding.
Topic Summary
Quantum numbers
Four quantum numbers are required to describe the distribution of electrons
in an atom; n, l, ml, and ms.
Electronic configuration
Electrons are arranged in orbitals following three rules; Pauli Exclusion
Principle, Hunds rule and Aufbau rules. The way electrons are arranged
determine the chemical properties of that particular element.
53
Periodic table trends
The trends in properties such as ionization energies and atomic radii can be
explained
in terms of the concepts of nuclear attraction, electron repulsions, shielding,
and
penetration.

1. What are quantum numbers? What information do we get from the
quantum numbers n, l, and m? We define a spin quantum number (ms), but
do we know that an electron literally spins?
2. Four blocks of elements in a periodic table refer to various atomic

orbitals being filled. What are the four blocks and the corresponding
orbitals? How do you get the energy ordering of the atomic orbitals
from the periodic table? What is the aufbau principle? Hund’s rule? The
Pauli Exclusion Principle? There are two common exceptions to the
ground-state electron configuration for elements 1–36 as predicted by
the periodic table. What are they?
54
3. The radius trend and the ionization energy trend are exact opposites.
Does this make sense? Define electron affinity. Electron affinity values
are both exothermic (negative) and endothermic (positive). However,
ionization energy values are always endothermic (positive). Explain.
4. Using the element phosphorus as an example, write the equation for a
process in which the energy change will correspond to the ionization
energy and to the electron affinity.
Explain why the first ionization energy tends to increase as one
proceeds from left to right across a period. Why is the first ionization
energy of aluminum lower than that of magnesium, and the first
ionization energy of sulfur lower than that of phosphorus?
Why do the successive ionization energies of an atom always increase?
5. What is the difference between core electrons and valence electrons?
Why do we emphasize the valence electrons in an atom when
discussing atomic properties? What is the relationship between valence
electrons and elements in the same group of the periodic table?
6. Give a possible set of values of the four quantum numbers for all the
electrons in a boron atom and a nitrogen atom if each is in the ground
state.
3.10 Activity
Students to attempt and discuss the questions in section 3.9.
55
CHAPTER FOUR: CHEMICAL BONDING
Topic Introduction
As we examine the world around us, we find it to be composed almost

entirely of
compounds and mixtures of compounds. The manner in which atoms are
bound together has a profound effect on chemical and physical properties.
Substances composed of unbound atoms do exist in nature, but they are
very rare. Molecular bonding and structure therefore play a central role in
determining the course of all chemical reactions, many of which are vital to
our survival. To understand the behavior of natural materials, we must
understand the nature of chemical bonding and the factors that control the
structures of compounds. In this topic we will present various classes of
compounds that illustrate the different types of bonds and then develop
models to describe the structure and bonding that characterize materials
found in nature.
Learning Outcomes
 List and describe the three types of chemical bonds found in chemical
substances.
 Discuss why atoms react with other atoms when its outermost shell is
only partly filled with electrons.
 Define the two types of ions and describe how ionic bonds form
between positive and negative ions.
 In a covalent bond, atoms share electrons. List several elements that
tend to form covalent bonds.
 Distinguish between a nonpolar covalent bond and a polar covalent
bond and give an example of each.
56
 Define hydrogen bond and describe conditions under which hydrogen
bonds form and cite one example.
 Explain what is meant by the polarity of the water molecule, and how
the polarity of water molecules allows them to interact with one
another.
Topic times
exercises: 3 hrs
Atoms are usually not capable of free existence but groups of atoms of
the same or different elements exist as one species, e.g., H2, O2, P4, S8,
H2O. A group of atoms existing together as one species and having
characteristic properties is called a molecule. Obviously, there must be some
force which holds these atoms together within the molecules
4.1 Chemical Bond

This force which holds the atoms together within a molecule is called a
chemical bond. Atoms bond because bonding lowers the potential energy
between positive and negative particles, whether those particles are
oppositely charged ions or atomic nuclei and electrons between them.
Types of Chemical Bonding
a) Electron transfer and ionic bonding: Ionic bonding occurs mainly
between atoms with a large difference in their tendency to lose or gain
electrons. These is mainly between metals (groups IA and 2A) and
non-metals (group VIIA and top of VIA). Electron transfer from metal
to non-metal occurs and each atom forms an ion with a noble gas
electron configuration. The electrostatic attraction between these
57
positive and negative ions draw them into a three dimensional array of
an ionic solid. The formula represents a cation-anion ratio (empirical
formula)
b) Electron sharing and covalent bonding: When two atoms have a small
difference in their tendency to lose or gain electrons, electron sharing
and covalent bonding is observed. The attraction of each nucleus for
the valence electrons of the other draws the atoms together. The
shared electron pair is localized between the two atoms.
c) Electron pooling and metallic bond: Metal atoms share their valence
electrons but in a different way from covalent bonding. In metallic
bonding, all the metal atoms in a sample pool their valence electrons
into an evenly distributed ‘sea’ of electrons that flow between and
around the metal-ion cores and attract them together. Electrons in
metallic bonding are delocalized, moving freely throughout the metal
piece.
4.2 Lewis Symbols & Structures
In the formation of a molecule, only the outer shell electrons are involved
and they are known as valence electrons. The inner shell electrons are well
protected and are generally not involved in the combination process. It is,
therefore, quite reasonable to consider the outer shell electrons, i.e., valence
shell electrons while discussing chemical bonds.
G.N. Lewis introduced simple symbols to denote the valence shell electrons
in an atom. The outer shell electrons are shown as dots surrounding the
symbol of the atom. These symbols are known as Lewis symbols or electron
dot symbols. These symbols ignore the inner shell electrons. A few examples
are given below:
58
Lewis structures depict the bonds between atoms of a molecule as well as
any un-bonded electron pairs. You can draw a Lewis dot structure for any
covalent molecule or coordination compound. Lines are drawn between
atoms to indicate chemical bonds. Single lines are single bonds. Double lines
are double bonds. Triple lines are triple bonds. (Sometimes pairs of dots are
used instead of lines, but this is uncommon.) Dots are drawn next to atoms
to show non-bonded electrons. A pair of dots is a pair of excess electrons.
Steps to Drawing a Lewis Structure
1. Pick a Central Atom
Start your structure by picking a central atom and writing its element
symbol. This atom will be the one with the lowest electronegativity.
Sometimes it's difficult to know which atom is the least
electronegative, but you can use the periodic table trends to help you
out. Electronegativity typically increases as you move from left to right
across the periodic table and decreases as you move down the table,
from top to bottom. You can consult a table of electronegativities, but
be aware different tables may give you slightly different values, since
electronegativity is calculated.
Once you have selected the central atom, write it down and connect
the other atoms to it with a single bond. You may change these bonds
to become double or triple bonds as you progress.
2. Count Electrons
Lewis electron dot structures show the valence electrons for each
atom. You don't need to worry about the total number of electrons,
only those in the the outer shells. The octet rule states that atoms with
8 electrons in their outer shell are stable. This rule applies well up to
59
period 4, when it takes 18 electrons to fill the outer orbitals. 32
electrons are required to fill the outer orbitals of electrons from period
6. However, most of the time you are asked to draw a Lewis structure,
you can stick with the octet rule.
3. Place Electrons around Atoms
Once you have determined how many electrons to draw around each
atom, start placing them on the structure. Start by placing one pair of
dots for each pair of valence electrons. Once the lone pairs are placed,
you may find some atoms, particularly the central atom, don't have a
complete octet of electrons. This indicates there are double or possibly
triple bonds. Remember, it takes a pair of electrons to form a bond.
4. If the compound is negatively charged, the magnitude of the charge

gives the number of additional electrons available for bonding. If the
compound has a positive charge, the magnitude of the charge gives
the number of electrons which must be removed from the number of
electrons available for bonding.
Lewis structures of some simple molecules
60
61
4.3 Ionic Bond
When a bond is formed by complete transference of electrons from one

atom to another so as to complete their outermost
orbits by acquiring 8 electrons (i.e., octet) or 2 electrons (i.e., duplet) in
case of hydrogen, lithium etc. and hence acquire the stable nearest noble
gas configuration, the bond formed is called ionic bond or electrovalent
bond.
Explanation of Ionic Bond
Atoms are electrically neutral. Therefore, they possess equal number of

protons and electrons. On losing an electron, an
atom becomes positively charged since now the number of protons
exceeds the number of electrons.
On the other hand, in case of atom, gaining the electron, the number of
electrons exceeds the number of protons and thus the atom becomes
negatively charged.
The oppositely charged particles formed above attract each other by

electrostatic forces of attraction. The bond thus formed is known as
electrovalent or ionic bond.
62
4.3.1 Electrovalency
The number of electrons lost or gained during the formation of an
electrovalent linkage is termed as the electrovalency of the element. For
example, sodium and calcium lost 1 and 2 electrons respectively and so their
valencies are 1 and 2. Similarly, chlorine and oxygen gain 1 and 2 electrons
respectively, so they possess an electrovalency of 1 and 2. In other words,
valency is equal to the charge on the ion.
4.3.2 Factors Governing the Formation of Ionic Bonds

(i) Ionisation Enthalpy (Ionization Energy)
63
Ionisation enthalpy of any element is the amount of energy required to
remove an electron from the outermost shell of an isolated atom in gaseous
phase so as to convert it into a gaseous positive ion. It is clear that lesser
the ionisation enthalpy, easier will be the removal of an electron, i.e.,
formation of a positive ion and hence greater the chances of formation of an
ionic bond. Ionisation enthalpy (I.E.) of alkali metals (i.e., group I elements)
is low, hence they have more tendency to form positive ions.
(ii) Electron Gain Enthalpy (Electron Affinity)
Electron affinity or Electron gain enthalpy of an element is the enthalpy
change that takes place when an extra electron is added to an isolated atom
in the gaseous phase to form a gaseous negative ion. Higher is the electron
affinity, more is the energy released and the more stable will be the
negative ion produced. Consequently, the probability of formation of ionic
bond will be enhanced. Halogens possess high electron affinity. So the
formation of their negative ions is very common, e.g., in case of chlorine,
electron affinity is +348 kJ/mole, i.e.,
(iii) Lattice Enthalpy (Lattice Energy)

In the formation of ionic compounds, the positively charged ions combine
with negatively charged ions to form the compound. The energy released
when the requisite number of gaseous
positive and negative ions combine to form one mole of the ionic compound
is called lattice enthalpy.
4.3.3 Properties of Ionic compounds

1. The solid is hard, rigid and brittle due to the strong attractive forces
that hold the ions in specific positions throughout the crystal.
64
2. Ionic compounds do not conduct electricity in the solid state but do
conduct when melted or when dissolved in water.
3. They have high melting and boiling points due the strong ionic
bonds.
4. They are only soluble in polar solvents like water
4.4 Covalent Bond

The bond formed between the two atoms by mutual sharing of
electrons between them so as to complete their octets or duplets in case of
elements having only one shell is called covalent bond or covalent linkage
and the number of electrons contributed by each atom is known as
covalency. The bond formed between the two atoms by mutual sharing of
electrons between them so as to complete their octets or duplets in case of
elements having only one shell is called covalent bond or covalent linkage
and the number of electrons contributed by each atom is known as
covalency.
65
66
67
4.4.1 Polar Covalent Bond
This is described as a polar bond. A polar bond is a covalent bond in which
there is a separation of charge between one end and the other - in other
words in which one end is slightly positive and the other slightly negative.
Examples include most covalent bonds. The hydrogen-chlorine bond in HCl
or the hydrogen-oxygen bonds in water are typical.
68
4.4.5 Intermolecular Forces in Covalent Compounds
(i) Weak Vander Waals Forces
These forces are due to temporary dipoles that are constantly created and
δ−¿¿ δ−¿¿
destroyed in covalent molecules. E.g. H δ +¿− H ¿

.----- H δ +¿− H ¿
. Weak attractive
forces holding H2 molecules together.
The weak Vander Waals forces tend to increase in magnitude with;
i) Increasing molecular mass

ii) Increasing number of electrons in a molecule
(ii) Dipole-Dipole Attractive Forces
69
If two covalent molecules differ in their electro negativities then permanent
dipoles are present.
δ−¿¿ δ−¿¿
H δ +¿−Cl ¿
.------- H δ +¿−Cl ¿
.permanent dipole-dipole attractive forces.
These forces are stronger than Vander Waals forces.
(iii) Hydrogen Bonding

1. Hydrogen must be directly bonded to a very electronegative element
e.g. N, O or F.
2. The electronegative element must also have lone pair(s) of electrons.
The more electronegative element attracts the bonded pair of
electrons to itself, thus exposing the nucleus of hydrogen. The exposed
nucleus of hydrogen then strongly attracts the negative charge of the
electronegative element in a neighboring molecule.
δ−¿¿ δ−¿¿
H δ +¿− F ¿
.------- H δ +¿− F ¿
.- hydrogen bonding
The strongly attractive forces bearing the dipoles of the above molecules is
called hydrogen bonding.
NB/
H-bonds are much stronger than dipole-dipole attractions and weak Vander
Waals forces.
70
The presence of H-bonds in molecules leads to intermolecular associations.
This leads to provision of high melting and boiling points to the molecules
e.g. group VII hydrides.
HF HCl HBr HI
19.9 -85.03 -66.72 -35.35
H-bonding enhances solubility in water for organic compounds.
Topic Summary
Chemical bonds
Hold groups of atoms together
Occur when a group of atoms can lower its total energy by aggregating
Types of chemical bonds
 Ionic: electrons are transferred to form ions

 Covalent: equal sharing of electrons
 Polar covalent: unequal electron sharing
Electronegativity: the relative ability of an atom to attract shared

electrons.
The polarity of a bond depends on the electronegativity difference of
the
bonded atoms.
The spacial arrangement of polar bonds in a molecule determines
whether the molecule has a dipole moment.
Lewis structures
Show how the valence electron pairs are arranged among the
atoms in a molecule
or polyatomic ion
71
Stable molecules usually contain atoms that have their valence
orbitals filled
Leads to a duet rule for hydrogen
Leads to an octet rule for second-row element
The atoms of elements in the third row and beyond can
exceed the octet rule


1. Give a rationale for the octet rule and the duet rule for H in
terms of orbitals. Give the steps for drawing a Lewis structure
for a molecule or ion. In general, molecules and ions always
follow the octet rule unless it is impossible. The three types of
exceptions are molecules/ions with too few electrons,
molecules/ions with an odd number of electrons, and
molecules/ions with too many electrons. Which atoms sometimes
have fewer than 8 electrons around them? Give an example.
Which atoms sometimes have more than 8 electrons around
them? Give some examples. Why are odd-electron species
generally very reactive and uncommon? Give an example of an
odd electron molecule.
72
2. What is meant by a chemical bond? Why do atoms form bonds
with each other? Why do some elements exist as molecules in
nature instead of as free atoms.
3. Some plant fertilizer compounds are (NH4)2SO4, Ca3(PO4)2, K2O,
P2O5, and KCl. Which of these compounds contain both ionic and
covalent bonds?
4.6 Activity
Students attempt and discuss the review questions in section 4.6.
73
TOPIC FIVE: THE KINETIC THEORY AND STATES OF
MATTER
Topic introduction
The three fundamental gas laws discover the relationship of pressure,
temperature, volume and amount of gas. Boyle's Law tells us that the
volume of gas increases as the pressure decreases. Charles' Law tells us that
the volume of gas increases as the temperature increases. And Avogadro's
Law tell us that the volume of gas increases as the amount of gas increases.
The ideal gas law is the combination of the three simple gas laws. In this
topic we will describe and deduce Boyles’ law, Charles law, Dalton’s law of
partial pressures, Grahams’ law of diffusion ideal and real gas laws. The
calculations using the gas law equations will also be carried out.
Learning outcomes
By the end of this topic, students should be able to;
1. State gas laws (Boyles’ law, Charles law, Dalton’s law of partial
pressures, Grahams’ law of diffusion ideal and real gas laws)
2. Describe the kinetic model of gases
3. Deduce the gas law equations from the kinetic equation
4. Compute calculations using the gas law equations
Topic times
-Compulsory online reading, activities, self-assessment and practice
exercises: 3 hrs
-Optional further reading: 1.5 hrs
-Total student input: 4.5 hrs
74
5.1 States of matter
Matter is anything that occupies space and has mass. There are three states
of matter.
Solid. Has definite volume and definite shape at a given temperature

and pressure. They are relatively rigid and the
constituents are held close together by strong attractive forces.
Liquid. Have definite volume but not definite shape. The molecules
constituting a liquid are held together by strong van der Waals forces
and other short range forces such as hydrogen bonds. Liquids flow and
can only take the shape of a container.
Gases. A gas has neither definite shape nor volume and molecular
forces of attraction are much weaker. Gases expand to fill any
container accessible to it.
Note that water undergoes all the three states of matter at given
temperatures. Consider the densities of the various phases of water.
Substances Temperature (˚C) Density (g/cm3)

Ice 0 0.91
Liquid 25 1.00
Steam 100 0.00059
SI units of common quantities
Mass – Kg
Length – m
75
Time – s
Force – N
Pressure – Nm-2, Pa, atmosphere (atm.), Torr, and mmHg
5.2 Introduction to Kinetic Theory of Gases

- The ideal gas equation describes how the gases behave but does not
explain why they behave the way they do. For instance, why does a
gas expand at constant pressure or why does its pressure increase
when the gas is compressed at constant temperature? To understand
these phenomena, the kinetic theory of gases was developed.
- Gases are composites of simple particles called molecules moving with
random motion. These gas molecules have energy given as, .

The gas movement is dependent on mass and velocity.
- In 1859, James Clark Maxwell and Ludwig Boltzmann contributed to
the knowledge of kinetic theory of gases. All gases obey the ideal gas
law at sufficiently low pressures. To understand the kinetic theory of
gases, we consider a model in which the gas molecules are in
constant, incessant motion, colliding with each other and with the
walls of the container it occupies.
- Because this model focuses on the motion of the molecules of a gas, it
is called the kinetic theory of gases.
5.2.1 Postulates of the kinetic theory of gases

i. A gas consists of a vast number of particles. The size of the gas
particles is negligible compared with the average distance between
them. This implies that the volume occupied by a gas is negligible,
compared to the volume of the container.
ii. The particles are always in continuous rapid motion in all directions
76
iii. The particles are continually undergoing collisions with each other
and with the walls of the vessel.
iv. The collision between the gas particles are perfectly elastic i.e.,
there is no loss in kinetic energy, Ek. Subsequently, the total kinetic
energy, Et, remains constant according to Boyle’s law,

.
v. The average kinetic energy of a molecule is proportional to the
absolute temperature. As the temperature increases, the frequency
of collision increases. This is called Charles’ law, .

vi. The duration of collision is negligible compared to the time between
collisions.
5.2.2 Assumptions for the Kinetic Theory of Gases

(a) The particles are so small compared to the distances between them
that the volume of the individual particles can be assumed to be
negligible.
(b) The attractive forces between the gas particles are negligible.
(c)All collisions between the gas particles and against the walls of the
container are perfectly elastic and there is no loss of energy during
collisions
A gas that conforms to the assumptions of the kinetic theory of gases is

called an ideal gas.
5.2.3 How Do Ideal Gases Differ from Real Gases?

A gas that confirms to the assumptions of the kinetic theory of gases is
called an ideal gas. It obeys the basic laws strictly under all conditions of
temperature and pressure.
The real gases such as hydrogen, oxygen, nitrogen etc., are

opposed to the assumptions (a), (b) and (c) stated above. Thus :
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a. The actual volume of molecules in an ideal gas is negligible,
while in a real gas it is appreciable.
b. There are no attractive forces between molecules in an ideal gas
while these exist in a real gas.
c. Molecular collisions in an ideal gas are perfectly elastic while it is
not so in a real gas.
For the reasons listed above, real gases obey the gas laws under
moderate conditions of
temperature and pressure. At very low temperature and very high
pressure, the clauses (a), (b) and (c) of kinetic theory do not hold.
Therefore, under these conditions the real gases show considerable
deviations from the ideal gas behaviour.
5.3 The Ideal Gas Laws

All perfect gases obey the ideal gas laws. Interestingly, all the ideal gas
equations can be derived from the kinetic theory of gases.
5.3.1 Boyle’s Law

It states that at constant temperature, the volume of a fixed mass of
gas is inversely
proportional to its pressure. If the pressure is doubled, the volume is
halved.
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Graphical representation of Boyle’s law
5.3.2 Charles’ Law
It states that at constant pressure, the volume of a fixed mass of gas
is directly proportional to the Kelvin temperature of absolute
temperature. If the absolute temperature is doubled, the volume is
doubled.
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Since the volume of a given mass of gas is directly proportional to the
Kelvin temperature, at the 0 K (-273 0C) there is no gas to talk about
as all gas will either have liquefied or solidified. This is absolute zero
where there is complete cessation of molecular motion.
Absolute zero is therefore the lowest temperature that is theoretically
possible characterized by complete absence of heat and motion.
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5.3.3 Combined Gas Law
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5.3.4 Avogadro’s Law
Equal volumes of gases at the same temperature and pressure contain equal
number of moles or molecules. If the molar amount is doubled, the volume
is doubled.
The Molar Gas Volume. It follows as a corollary of Avogadro’s Law that

one mole of any gas at a given temperature (T) and pressure (P) has the
same fixed volume. It is called the molar gas volume or molar volume. In
order to compare the molar volumes of gases, chemists use a fixed
reference temperature and pressure. This is called standard temperature and
pressure (abbreviated, STP). The standard temperature used is 273 K (0°C)
and the standard pressure is 1 atm (760 mm Hg). At STP we find
experimentally that one mole of any gas occupies a volume of 22.4 litres i.e.
5.3.5 The Ideal Gas Equation
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Also called the Universal Gas Law. It applies to all gases which exhibit ideal
behaviour i.e., obey the gas laws perfectly. The ideal gas law may be stated
as : the volume of a given amount of gas is directly proportional to the
number of moles of gas, directly proportional to the temperature, and
inversely proportional to the pressure. Introducing the proportionality
constant R in the expression (1), it becomes;
NB: 1. If V is in Liters, P in atmospheres and T in Kelvin, then the value of R

would be 0.082atmLmol-1K-1.
2. If V is in M 3, P in NM-2 and T in Kelvin, the value of R would be

8.31Jmol-1K-1.
Example #1: Determine the volume of occupied by 2.34 grams of carbon

dioxide gas at STP.
Solution:
83
1) Rearrange PV = nRT to this:
V = nRT / P
2) Substitute:
V = [(2.34 g / 44.0 g mol¯1) (0.08206 L atm mol¯1 K¯1) (273.0 K)] / 1.00
atm
V = 1.19 L (to three significant figures)
Example #2: 5.600 g of solid CO2 is put in an empty sealed 4.00 L

container at a temperature of 300 K. When all the solid CO2 becomes gas,
what will be the pressure in the container?
Solution:
1) Determine moles of CO2:
5.600 g / 44.009 g/mol = 0.1272467 mol
2) Use PV = nRT
(P) (4.00 L) = (0.1272467 mol) (0.08206 L atm mol¯1 K¯1) (300 K)
P = 0.7831 atm (to four sig figs)
5.4 Imperfect Gases (Real Gases)
Although the ideal gas equation is a very useful description for

gases, all real gases fail to obey the relationship to a greater or a lesser
extent. Real gases obey the ideal gas equation only at low pressure and high
temperature. Under these conditions, all gases behave ideally except for He
and CO2, which are slightly disobedient. However, these conditions are not
easily achieved due to the fact that
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i. At high pressure and high density, the intermolecular forces are not
negligible.
ii. Due to intermolecular forces of attraction the volume of a gas
cannot be ignored
The calculated properties of the perfect gas of the kinetic theory are the
same as the experimental properties of the ideal gas thermodynamics. It
might be expected that the extension and modification of the simplified
model of the perfect gas should provide and explanation for observed
deviations from ideal gas behavior. The first improvement of the model is to
abandon the assumption that the volume of the molecules themselves can
be completely ignored in comparison with the volume of the container the
gas occupies. Hence V-nb should be the volume correction. Where the ‘b’
parameter represents the excluded volume occupied by gas molecules. The
non-zero volume of molecules implies that instead of moving in a volume V,
they are instead restricted to a smaller volume V-nb where ‘nb’ is
approximately the total volume taken up by the molecules themselves. This
is referred to as corrected volume or co-volume.
A second correction to the ideal (perfect) gas formula comes from the
consideration of the forces of cohesion between the gas molecules. The
extent of deviation can be seen by slightly rearranging the ideal gas
equation.
If the ideal gas equation were always true under all conditions,
then at all times. But we know this is not so hence we need to

modify the equation. The repulsive interactions between molecules are taken
into account by supposing that they cause the molecules to behave as small
but impenetrable spheres. The pressure correction due to the intermolecular
forces of attraction is given as
85
. This means that the Van der Waal’s equation for real gases
becomes:
or
The Van der Waal’s constants ‘a’ and ‘b’ are different for each gas.
‘a’ indicates the magnitude of cohesive forces between molecules of a gas

during collision
‘b’ is a measure of actual volume occupied by the gas. Note that b increases
with increase in molecular mass of a gas.
The Van der Waal’s equation was developed by Johannes Van der Waal’s in
1873.
86
5.5 Dalton’s Law of Partial Pressures
The total pressure of a mixture of gases is equal to the sum of the partial
pressures of all the gases present.
87
Topic Summary
Bulk matter can exist in three states: gas, liquid, and solid. Gases have the
lowest density of the three, are highly compressible, and fill their containers
completely. Elements that exist as gases at room temperature and pressure,
are clustered on the right side of the periodic table; they occur as either
monatomic gases (the noble gases) or diatomic molecules (some halogens,
N₂, O₂).
 Gases expand spontaneously to fill containers in which they are held,

equaling their volume. Consequently, they are highly compressible.
 Gases form homogeneous mixtures with each other regardless of the
identities or relative proportions of the component gases
88
 The characteristic properties of gases arise because the individual
molecules are relatively far apart, hence, acting largely as though they
were alone.
The volume of a gas is inversely proportional to its pressure and directly

proportional to its temperature and the amount of gas. Boyle showed that
the volume of a sample of a gas is inversely proportional to pressure
(Boyle’s law), Charles and Gay-Lussac demonstrated that the volume of a
gas is directly proportional to its temperature at constant pressure (Charles’s
law), and Avogadro showed that the volume of a gas is directly proportional
to the number of moles of gas (Avogadro’s law).
The empirical relationships among the volume, the temperature, the

pressure, and the amount of a gas can be combined into the ideal gas law,
PV = nRT. The proportionality constant, R, is called the gas constant. The
ideal gas law describes the behavior of an ideal gas, a hypothetical
substance whose behavior can be explained quantitatively by the ideal gas
law and the kinetic molecular theory of gases. Standard temperature and
pressure (STP) is 0°C and 1 atm respectively.
The Gas constant (R) is the constant of proportionality in the ideal-gas

equation. Some values of R, are given below;
Unit Value
L-atm/mol-K 0.08206
Cal/mol-K 1.987
J/mol-K 8.314
M3-Pa/mol-K 8.314
L-torr/mol-K 62.36
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1. Arun Bahl: Essentials of Physical Chemistry,
Multicolor Edition
2. Robert G. Mortimer: Physical Chemistry, Third Edition

1. A sample of nitrogen has a volume of 80.46 mL at 50 ˚C. What
volume will the sample occupy at 0 ˚C if the pressure is kept
constant? (Ans = 67.95 mL).
2. A mixture consisting of 28 g of N 2 and 64 g of O2 occupies a
volume of 8.314 x 10-3 m3 at 300 K. Calculate.
(a) The mole fraction of each gas (Ans, = 1/3 for N 2 and
2/3 for O2)
(b) The total pressure exerted by the gaseous mixture
(Ans = 9.0 x 105 N/M2)
(c)The partial pressure of each gas in the mixture (Ans. P N2 =
3.0 x 105 N/M2 and PO2 = 6.0 x 105 N/M2)
3. A meteorogist fills a weather observation balloon with hydrogen
at a pressure of 1 atm. at room temperature. If the volume of
the balloon is 30 Liters on the ground. What will its pressure be
at an altitude of 18 km where the temperature is -50 ˚C and
pressure is 0.1 atm.? (Ans = 224 liters).
4. A cylinder in a gasoline engine initially has a volume of 0.5 Liters
and contains gases that exert pressure at 1 atm. What is the
pressure of the gases when the volume of the cylinder is reduced
to 0.2 liters? (Ans = 2.5 atm).
5. 20.83 g of a gas occupies 4.167 L at 79.97 kPa at 30.0 °C. What
is its molecular weight?
5.9 Activity
Students should attempt the questions in section 5.8
90
TOPIC SIX: RATES OF A REACTION
Topic introduction
The Reaction Rate for a given chemical reaction is the measure of the
change in concentration of the reactants or the change in concentration of
the products per unit time. The speed of a chemical reaction may be defined
as the change in concentration of a substance divided by the time interval
during which this change is observed. During the course of a reaction
A+B⟶AB, reactants A and B are consumed while the concentration of
product AB increases. The reaction rate can be determined by measuring
how fast the concentration of A or B decreases, or by how fast the
concentration of AB increases. In this topic we will find out what the rate of
reaction is, describe the factors that affect the rate of a reaction and
compute the rate equation as well as, the rate constant.
Learning outcomes
 Understand rate of reaction and factors affecting rate of reaction
 Calculate the rate equation and the rate constant
Topic times
 Compulsory online reading, activities, self-assessment and
practice exercises: 3 hrs
6.0 Rate of Reaction

During a chemical reaction, the concentration of the reactants decreases and
the concentration of the products increases; the rate of a reaction is the
decrease in concentration of reactants per unit time, or the increase in
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concentration of products per unit time; the units of rate of reaction are
moldm-3s-1
The rate of increase or decrease of concentration depends on the
stoichiometric coefficients;
In the reaction:
A + 3B ➔ 2C + 4D
The rate of increase in the concentration of C will be double the rate of
decrease in the concentration of A
The rate of decrease in the concentration of B will be three times the rate of
decrease in the concentration of A. The rate of reaction is defined as the
change in concentration per unit time for a species with a stoichiometric
coefficient of 1
6.1 Measuring Rates of Reaction
The rate of a reaction is not constant over time; as the reaction proceeds,
the concentration of reactants decrease and so the collision frequency
decreases, slowing down the reaction; it is possible to measure the rate of
reaction at any point during a reaction by measuring the change in
concentration of the reactants over time and plotting a concentration-time
graph:
A typical concentration-time graph would look like this:
(E.g. for the reaction SO2Cl2 → SO2 + Cl2)
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The rate of reaction is the change in concentration per unit time and can
therefore be calculated from the gradient of the line at a particular time
As the graph is a curve (its gradient is steadily decreasing with time), the
gradient of the line at a particular point must be calculated by drawing a
tangent to that line at a particular point and calculating the gradient of the
tangent
The initial rate of reaction is the gradient of the tangent to the curve at t =
0.
The rate of reaction at a particular time is the gradient of the tangent to the
curve at that particular time
In some reactions, it is not easy to measure the concentration of a reactant
over a time period; it is often easier to mention the time taken for a
particular stage in the reaction to be reached; since rate is the change in
concentration per unit time, it follows that the rate of reaction is inversely
proportional to the time taken for that stage to be reached; examples of
such measurements could be:
- Time taken for fixed amount of gas to be produced
- Time taken for absorbance to change by a certain amount
- Use of a clock reaction: the appearance of a certain colored product is
delayed by adding a fixed amount of another species:
93
Eg S2O82-(aq) + 2I(aq) → 2SO4 (aq) + I2(aq)
Iodine is produced in this reaction; if starch was added to the original
mixture, a blue-black colour would appear immediately however if a fixed
amount (ie 0.02 moles) of sodium thiosulphate is also added to the mixture,
it reacts with the iodine and a blue-black colour is only seen when all the
thiosulphate has been used up it is possible to measure the time taken for
the blue-black colour to appear
6.2 Simple Collision Theory
Substances in the liquid, aqueous and gaseous phase consist of particles in
rapid and constant motion; the rate of a chemical reaction depends on three
factors:
(i) Collision frequency: a chemical reaction is to take place between two
particles, they must first collide; the number of collisions between particles
per unit time in a system is known as the collision frequency of the
system; the collision frequency of a system can be altered by changing the
concentration of the reactants, by changing the total pressure, by changing
the temperature or by changing the size of the reacting particles
(ii) Collision energy: not all collisions result in a chemical reaction; most
collisions just result in the colliding particles bouncing off each other;
collisions which do not result in a reaction are known as unsuccessful
collisions; unsuccessful collisions happen when the colliding species do not
have enough energy to break the necessary bonds in the reacting particles;
if the colliding species do have sufficient energy, they will react and the
collision will be successful; the combined energy of the colliding particles is
known as the collision energy
Not all the particles in a given system have the same energy; they have a
broad distribution of different energies; the shape of the distribution of
energies depends on the temperature of the system: the higher the
94
temperature, the greater the mean kinetic energy of the particles; the
distribution of molecular energies at a characteristic temperature T1 can be
represented graphically - it is known as a Maxwell-Boltzmann
distribution:
At a higher temperature T2 the distribution of energies will be different; the

mean energy will be higher and the distribution will be broader:
The greater the mean kinetic energy of the particles, the greater the collision
energy
(iii) Activation energy: the minimum energy the colliding particles need in
order to react is known as the activation energy; if the collision energy of
the colliding particles is less than the activation energy, the collision will be
unsuccessful; if the collision energy is equal to or greater than the activation
95
energy, the collision will be successful and a reaction will take place; the
activation energy can be changed by the addition of a catalyst
The fraction of successful collisions can be shown graphically as the area
under the curve to the right of the activation energy divided by the total
area under the distribution curve:
6.3 Factors affecting the rate of a chemical reaction

The rate of a chemical reaction can be changed in a number of ways:
i) By changing the concentration of the reacting particles
ii) By changing the pressure of the system (if some of the reacting
particles are in the gas phase)
iii) By changing the temperature of the system
iv) By adding a catalyst
(i) Concentration:
The greater the concentration of the species in a liquid or gaseous mixture,
the greater the number of species per unit volume and the greater the
frequency with which they will collide; hence an increase in concentration
causes the rate of reaction to increase by increasing the collision frequency
Changing the concentration has no effect on the collision energy or the
activation energy, and hence no effect of the fraction of successful collisions
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So an increase in concentration increases the rate of reaction because the
number of particles per unit volume increases so the collision
frequency increases
(ii) Pressure
The greater the pressure in a gaseous mixture, the greater the number of
species per unit volume and the greater the frequency with which they will
collide; hence an increase in pressure causes the rate of reaction to increase
by increasing the collision frequency; the pressure of a system is generally
increased by reducing its volume
Changing the pressure has no effect on the collision energy or the activation
energy, and hence no effect on the fraction of successful collisions
So an increase in pressure increases the rate of reaction because the
number of particles per unit volume increases so the collision
frequency increases
(iii) Temperature
An increase in temperature changes the distribution of molecular energies in
such a way as to increase the mean kinetic energy of the particles and thus
increase the collision energy
For a given activation energy, it follows that an increase in temperature will
increase the number of colliding particles with an energy equal to or greater
than the activation energy (i.e. the shaded area under the graph to the right
of the activation energy):
97
It is clear that at a higher temperature, the fraction of particles with enough
energy to react increases significantly and therefore the fraction of collisions
which are successful thus also increases
An increase in temperature also increases the collision frequency, because
they are moving faster; this also increases the rate of reaction
(iv)Catalysts
A catalyst is a substance which changes the rate of a chemical reaction
without itself being chemically altered at the end of the reaction. Catalysts
provide an alternative reaction pathway, usually by introducing an extra step
into the reaction, which has a lower activation energy than the uncatalysed
reaction.
Since catalysts reduce the activation energy of a chemical reaction, the
number of particles which have sufficient energy to react will therefore
increase; this can be shown graphically by considering the Maxwell-
Boltzmann distribution of molecular energies:
98
A catalyst increases the rate of reaction because the activation energy of the
particles decreases, so more of the particles have a collision energy greater
than the activation energy, so the fraction of successful collisions increases
A catalyst has no effect on the collision frequency or the collision energy
(v) Physical states of reactants
If reactants are gaseous, or well mixed in liquid or aqueous form, then all of
the particles in the sample are able to react
Particles in the solid state, however, are not free to move, so only the
particles at the surface of the solid are able to collide with other particles;
this reduces the collision frequency and reduces the rate of reaction
The rate of reaction in solids can be increased by reducing the particle size,
and hence increasing the surface area exposed to collisions:
99
A – Large particle size, fewer of the blue solid particles can collide with the
red particles, slower reaction
B – Small particle size, more of the blue solid particles can collide with the
red particles, faster reaction
6.4 Orders of Reaction and Rate Equations
(a) Introducing Rate Equations
The relationship between the rate of a chemical reaction and the
concentration of the reactants is shown by the rate equation of the
reaction
Consider the reaction A + 3B → 2C + 4D
The rate of this chemical reaction is given by the equation: rate = [A] x [B]y
[A] is the concentration of A, and [B] is the concentration of B.
- x and y are the orders of reaction with respect to A and B respectively.
The order of reaction with respect to a given reactant is the power of that
reactant's concentration in the rate equation.
The sum of these powers, in this case x + y, is known as the overall order of
reaction:
The overall order of reaction is the sum of the powers of the reactant
concentrations in the rate equation
k is the rate constant of the reaction.
The rate constant is the constant of proportionality in the rate equation

(b) Determining orders of reaction from initial rate measurements
100
The orders of reaction with respect to each reactant in the reaction can be
determined by carrying out the reaction with various different initial
concentrations and measuring the change in initial rate of reaction; the
orders of reaction can be determined arithmetically or graphically
If the order of reaction with respect to one reactant is being determined, the
concentration of one reactant only should change; the others should remain
constant so that the change in rate can be attributed to the change in
concentration of that reactant alone; if the overall order is being determined,
the concentration of all reactants should change by the same factor
6.5 The Rate equation and the Rate constant
(Change in concentration) order of reaction = change in rate
If the reaction is first order, then if the concentration doubles the rate will
also double; if the concentration triples the rate will also triple, etc
If the reaction is second order, then if the concentration doubles the rate will
quadruple. If the concentration triples the rate will increase ninefold, etc
If the reaction is zero order, then the change in concentration will have no
effect on the rate of reaction
Example 1:
Consider the reaction RX + OH- → ROH + X-
The following rate data were obtained at constant temperature; what is the
rate equation and what is the rate constant
Solution:
- From expt 2 to expt 1, the concentration of hydroxide ions doubles and the
concentration of RX is unchanged; the rate also doubles, so the order of
reaction with respect to OH- is 1
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- From expt 3 to expt 1, the concentration of RX doubles and the
concentration of hydroxide ions is unchanged; the rate also doubles, so the
order of reaction with respect to RX is also 1.
The rate equation can thus be written as follows: rate = k[RX][OH-]
Having deduced the rate equation, the rate constant can be calculated using
the data in one of the experiments:
E.g. in expt 1, k = rate/([RX][OH-]) = 8 x 10-3/(0.04 x 0.01) = 20 mol -
1
dm3s-1
Example 2:
Consider the reaction PCl3 + Cl2 → PCl5
The following rate data were obtained at constant temperature; what is the
rate equation and what is the rate constant?
Solution:
- From expt 1 to expt 2, the concentration of PCl3 doubles and the
concentration of Cl2 is unchanged; the rate also doubles, so the order of
reaction with respect to PCl3 is 1
- From expt 2 to expt 3, the concentration of both reactants doubles; the
rate increases eightfold, so the overall order of reaction is 3
- The order of reaction with respect to chlorine is therefore 3 – 1 = 2
The rate equation can thus be written as follows: rate = k[PCl][Cl]2
So using Expt 1, k = rate/[PCl3][Cl2]2 = 0.0004/(0.2 x 0.12)= 0.2 mol-
2
dm6s-1
6.6 Explaining orders of reaction
The orders of reaction for a chemical equation are not always the same as
the reaction coefficients:
102
E.g.
The reaction NO2 + H2 → NO + H2O has the following rate equation: rate =
k[NO2]2
It is therefore not possible to predict the rate equation of a reaction simply
by looking at the reaction coefficients
Many reactions consist of a series of different steps, some of which are slow
and some of which are very fast; it is the slowest step in a chemical reaction
which determines how fast a reaction is; for this reason the slowest step in a
chemical reaction is called the rate-determining step; changing the rate of
this step will affect the overall rate of reaction; changing the rate of fast
steps won’t
E.g.
Consider the reaction NO2 + H2 → NO + H2O
This reaction happens in two steps:
Step 1: NO2 + NO2 → NO3 + NO this step is slow
Step 2: NO3 + H2 → NO2 + H2O this step is fast
The order of reaction with respect to NO2 and H2 can be predicted as follows:
- Step 1 is the slowest step and is therefore the rate-determining step
- This step involves two molecules of NO 2, and so doubling the concentration
of NO2 will make collisions in this step four times more likely
- So the reaction is second order with respect to NO2
- H2 is not involved in this step; it is only involved in the second, fast step
- changing the concentration of H 2 therefore has no effect on the rate of
reaction, and the reaction is zero order with respect to H 2
Topic Summary
In reactions that do not happen instantaneously, most collisions are

unsuccessful. Such reactions can be made faster by increasing the collision
frequency (the more frequently the particles collide, the faster the reaction
will be) such reactions can also be made faster by increasing the fraction of
103
successful collisions (the greater the fraction of collisions that result in a
chemical reaction, the faster the reaction will be); this can be achieved
either by increasing the collision energy or by reducing the activation
energy.
The rate of reaction increases when the temperature is increased because
the collision frequency and the collision energy both increase; of these two
reasons, the increase in collision energy is the most important and accounts
for about 95% of the increase in rate for a given reaction; increasing the
temperature has no effect on the activation energy
An increase in temperature increases the rate of reaction because the mean
collision energy of the particles increases, so more of the particles have a
collision energy greater than the activation energy, so the fraction of
successful collisions increases; also the particles are moving faster so the
collision frequency increases
6.7 Further Reading/ References
1. Arun Bahl: Essentials of Physical Chemistry, Multicolor
Edition

1. Explain the meaning of a successful collision
2. Describe the factors affecting the rate of a reaction
3. For the reaction
A(g) + B(g) + C(g) → D(g)
the following data were obtained at constant temperature
Expt Initial [A] Initial [B] Initial [C] Initial

(mol/L) (mol/L (mol/L) Rate(mol/L.s
104
1 0.0500 0.0500 0.0100
6.25x10-3
2 0.100 0.0500 0.0100 1.25x10-2
3 0.100 0.1000 0.0100 5.00x10-2
4 0.0500 0.0500 0.0200 6.25x10-3
i. What is the order with respect to each reactant?
ii. Write the rate law.

iii. Calculate k (using the data from experiment 1)
4. Using the following data, for the reaction below;
A + 5B + 6C → 3D + 3E
Experiment [A] (M) [B] (M) [C] (M) Initial Rate

(M/s)
1 0.35 0.35 0.35 8.0 x 10-4
2 0.70 0.35 0.35 3.2 x 10-3
3 0.70 0.70 0.35 6.4 x 10-3
4 0.70 0.35 0.70 3.2 x 10-3
i. What is the order with respect to each reactant?
ii. Write the rate law.

iii. Calculate k (using the data from experiment 3)
105
6.9 Activity
Students should attempt the review questions in section 6.8.
TOPIC SEVEN: CHEMICAL EQUILIBRIUM

Topic introduction
Chemical change is one of the two central concepts of central science, the
other being structure. The origin of chemistry itself is rooted in the
observation of transformations such as the combustion of wood, the winning
of metals from their ores and freezing of water, an experience that human
beings experience daily. Chemical change occurs when the atoms that make
up one or more substances rearrange in such a way that new substances are
formed. These substances are components of a chemical reaction system;
the components which decrease in quantity are reactants while those which
increase in quantity are products. When a chemical reaction takes place in a
container which prevents the entry or escape of any substances involved in
the reaction, the quantities of these components change as some are
consumed and others are formed. Eventually, this change will come to an
end, after which the composition will remain unchanged as long as the
system remains undisturbed. This change is then said to be at equilibrium.
In this topic we will describe; factors that affect equilibrium, equilibrium laws
and equilibrium constants, acids and bases, pH of solutions, solubility and
solubility products, hydrolysis of salts, indicators and buffers.
Learning outcomes
 Describe a system at chemical equilibrium
 Describe the law of chemical equilibrium (law of mass action)
 Write an equilibrium constant expression for a reversible reaction
in terms of reactants and product concentration or partial
pressures (gases)
106
 Calculate the value of equilibrium constant for a reversible reaction
given the equilibrium concentrations of all reactants and products
 Calculate the value of Kc given Kp and vice varsa
 Explain the differences between weak and strong bases
 Determine the relationship between the strength of an acid and its
conjugate base and be able to calculate Kb given Ka and vice varsa
 How to make a buffer solution and its properties
 The application of acids and buffers in daily life
 To calculate the solubility product of soluble ionic solids
Topic times
 -Compulsory online reading, activities, self-assessment and
7.0 Introduction to Chemical Equilibrium
Chemical equilibrium is a state of balance at which the rate of forward
reaction is ideally equal to the rate of backward reaction. At equilibrium,
chemical position of a reactant and the product are constant as long as the
pressure and temperature are not altered. Chemical reactions are said to be
dynamic in that molecular reactions take place at a micro level i.e. both the
forward and the backward reactions take place simultaneously at molecular
level. The macro-properties such as pressure, volume and temperature
remain constant.
Reversible reactions – Any reactions that take place in either direction

(forward and backward) is said to be reversible and is denoted by the
symbol . All reversible reactions reach a state of chemical

equilibrium i.e. a state at which no further change in chemical composition of
107
the reaction mixture takes place unless an external disturbance such as
change in temperature or concentration is applied into the system.
Le Châtelier’s Principle – It states that if a stress is applied to a system in

equilibrium, the system will adjust itself in such a way as to remove or undo
(minimize) the stress. The reaction proceeds in the direction that offsets the
change in conditions.
The effect of changing pressure, temperature, and concentration on

equilibrium position can be described qualitatively using Le Châtelier’s
principle.
7.1 Factors affecting equilibrium position

1. Pressure – The effect of pressure is minimal in solids and liquid
systems but very significant in gaseous equilibria. Consider the
reaction for the manufacture of ammonia in the Haber process
N2 (g) + 3H2 (g) 2NH3 (g)

An increase in pressure will favour the forward reaction because
increased pressure results in decreased volume and hence the reaction
will move in the direction which favours a decrease in volume. This is
in accordance with Boyle’s law i.e. .

2. Temperature – Increase in temperature favours an endothermic
reaction while decrease in temperature favours an exothermic system.
Any reaction giving out heat can be reversed by making it absorb heat
by addition of heat (Increasing the temperature). Increasing the
temperature of an exothermic system favours the dissociation of
products. Consider the contact process reaction
1
SO2 ( g)  O 2 SO 3 ( g ) H  v e
2 (g)
108
Increase in temperature favours the backward reaction while decrease
in temperature favours the forward reaction.
3. Concentration – Increasing the concentration of any of the species of

a system at equilibrium will make the reaction to move in the direction
in which the concentration of the species has been increased. Consider
the following hypothetical reaction
Increasing the concentration of D will favour the backward reaction as

more of C and D react to form more of A and B. The reaction between
steel wool and steam is a good example of a reaction exhibiting
equilibrium characteristics.
Removal of H2 as soon as it is formed favours the forward reaction. For

gaseous systems, pressure is a measure of concentration.
4. Catalyst – A catalyst does not affect equilibrium position, but it

ascertains that it is achieved earlier or later. Consider the contact
process, where vanadium pentoxide or platinum catalyst is used.
500 C
2 SO 2 ( g )  O 2 ( g ) 2 SO 3 ( g ) 2 hrs
500 C
2 SO 2 ( g )  O 2 ( g ) 2 SO 3 ( g ) 30 mins
catalyst
A catalyst can enhance the time within which equilibrium is can be

achieved.
7.2 Equilibrium Law and Equilibrium Constants
109
Consider a hypothetical reaction
It follows that
Introducing the rate constants then:
At equilibrium, , so that
but
where is the equilibrium constant.

The Law of mass action – It states that the rate of a chemical
reaction is directly proportional to the concentration of the reacting
species raised to their concentration terms (coefficients) at constant
temperature i.e.
Equilibrium Law – It states that the product of the concentration of

the products each raised to the power of the number of moles of each
110
species participating divided by the product of the concentration of the
reactants each raised to the power of the number of moles of the
species participating is a constant i.e.
7.3 Ways of expressing equilibrium
i) In terms of concentration, is used
ii) In terms of partial pressures, is used
iii) In terms of dissociation constant, is used
iv) In terms of acid-base dissociation/ionization, and are

used
v) In terms of mole fraction, is used
and expressions
Consider the following reaction at equilibrium;
Solution
, the units of will be determined thus
Kc 
m ol dm 3 2
 no units
m ol dm 3 . m ol dm 3
111
For
and the units can be determined as follows
7.4 Features of equilibrium constant

i. Applies to systems at equilibrium
ii. Changes with change in temperature
iii. Unaffected by concentration changes
iv. It is an indication as to what extent the reaction takes place
v. Gives no information about the rates of a reaction
7.5 The relationship between Kc and Kp

Consider a hypothetical reaction of the form
The Kp for the raction is written thus
but from the ideal gas equation and
Therefore:
112
Recall that is concentration so that the term in will be Kc. This implies
that:-
But (c+d)-(a+b) = change in moles from the RHS to the LHS, denoted as
Δn, hence
The equilibrium constant can also be written in terms of mole fraction x. This
equilibrium constant is called Kx and for a reaction of the form:
It can also be shown (refer to class notes) that
and therefore
If dn =0, then
For dn ≠ 0
We have
7.6 Ionization of Acids and Bases

Arrhenius concept of acids and bases – In 1884, Arrhenius defined an
acid as any substance that can increase the concentration of H + in aqueous
–
solution while a base is a substance which increases the OH ion
concentration. Namely, if an acid is HA and base BOH then
113
and . Therefore, when an acid and a base react, water if
formed.
Brϕnsted-Lowry concept of acids and bases – In 1923, Brϕnsted and

Lowry defined an acid as a substance that is able to donate a proton to some
other while a base is substance that is able to accept a proton from an acid.
Another good example of a Brϕnsted-Lowry acid-base pair is:
This means that water can either be a base or an acid.
The strength of an acid is determined by tendency to give up a proton while

the strength of a base is determined by its tendency to receive or accept a
proton.
Lewis concept of acids and bases - Whereas the concept of Brønsted acid
and base is limited to the transfer of protons, a Lewis acid A is generally
defined as an acceptor, and a Lewis base B a donor, of an electron pair. An
acid A and a base :B bind together to form an adduct A:B. For example, a
114
Lewis acid BF and a Lewis base OEt (diethylether) form an adduct
3 2
F B:OEt . The stability increases by the completion of an octet around boron

3 2
when such an adduct forms. The stability of an adduct is expressed by the
equilibrium constant of the reaction.
Kf
A + B A-B
Therefore, the Lewis acidities of a series of acids are measured by comparing
K against a common base :B. Since a proton is also an electron acceptor,

f
Brønsted acids are the special case of the more general Lewis definition of
acids . According to this definition, a co-ordinate bond in a transition metal
complex is also an acid-base reaction of a ligand (Lewis base) with a metal
center (Lewis acid).
Example: Write the reaction between ammonia and boron trifluoride and
giving reasons explain which is a Lewis acid or Lewis base.
7.7 The pH of a solution
This is defined as the negative logarithm to base 10 of the ion concentration.
The ionization of water
The equilibrium constant for the reaction is given as:
115
Therefore
The product is called the ionic product of water:
The ionic product of water Kw has a value of 10-4 mol2 L-2 at room
temperature. The ionic product of water is therefore temperature dependent.
When water is pure (completely neutral solution) then:-
= 10-7mol L-1. In acidic or basic solution, the product
remains constant.
Ionization of strong acids – Strong acids and strong bases ionize

completely and no equilibrium is established.
Example
Calculate the pH of a 0.00013 M HCl.
Soln.
The concentration of H3O+ = 0.00013
116
pH = 3.9
7.8 Indicators
Indicators are substances whose solutions change color due to changes in
pH. These are called acid-base indicators. They are usually weak acids or
bases, but their conjugate base or acid forms have different colors due to
differences in their absorption spectra.
List of common indicators in the table below;
Name of Acid color Base color pH range of color

Indicator change
Methyl violet Yellow Blue 0.0-1.6
Thymol blue Red Yellow 1.2-2.8
Methyl orange Red Yellow 3.2-4.4
Bromocresol Yellow Blue 3.8-5.4

green
Methyl red Red Yellow 4.8-6.0
Litmus Red Blue 5.0-8.0
Bromothymol Yellow Blue 6.0-7.6

blue
Phenolphthalein Colorless Pink 8.2-10
Thymolphthalein Colorless Blue 9.4-10.6
Alizarin yellow R Yellow Red 10.1-12.0
117
Indicators are organic weak acids or bases with complicated structures. For
simplicity, we represent a general indicator by the formula HIn and its
ionization in a solution by the equilibrium,
HIn⇌H++In−
And, define the equilibrium constant as Kai,
which can be rearranged to give
When [H+] is greater than 10 Kai, In− color dominates, whereas color due to
HIn dominates if [H+]<Kai/10. The above equation indicates that the color
change is the most sensitive when [H+]=Kai in numerical value.
We define pKai = - log(Kai), and the pKai value is also the pH value at which
the color of the indicator is most sensitive to pH changes.
Taking the negative log of Kai gives,
Note that pH = pKai when [In−]=[HIn]
118
In other words, when the pH is the same as pKai, there are equal amounts of
acid and base forms. When the two forms have equal concentration, the
color change is most noticeable.
Colors of substances make the world a wonderful place. Because of the

colors and structures, flowers, plants, animals, and minerals show their
unique characters. Many indicators are extracted from plants. For example,
red cabbage juice and tea pigments show different colors when the pH is
different. The color of tea darkens in a basic solution, but the color becomes
lighter when lemon juice is added. Red cabbage juice turns blue in a basic
solution, but it shows a distinct red color in an acidic solution.
7.9 Hydrolysis
Basic Salts
Let us consider the behavior of anions first. Anions of weak acids react with
proton sources. When placed in water these anions react to some extent
with water to accept protons and generate OH - ions and thus cause the
solution pH to be greater than 7. Recall that proton acceptors are Bronsted-
Lowry bases. Thus, the anions of weak acids are basic in two senses: They
are proton acceptors, and their aqueous solutions have pH's above 7. The
nitrite ion, for example, reacts with water to increase the concentration of
OH-ions:
This reaction of the nitrite ion is similar to that of weak bases such
as NH3 with water:
Thus, both NH3 and N02 - are bases and as such have a basicity
or base dissociation constant, Kb, associated with their
119
corresponding equilibria. According to the Bronsted-Lowry theory,
the nitrite ion is the conjugate base of nitrous acid. Let's consider the
-
conjugate acid-base pair HN02 and N02 and their behavior in
water
Where Kw is the ion product constant of water
Thus, the product of the acid-dissociation constant f o r an acid and

the base-dissociation constant for its conjugate base is the ion-
product constant for water:
[1]
Knowing the Ka for a weak acid, we can easily find the Kb for the anion
of the acid:
Kw
Kb=
Ka
By consulting a table of dissociation constants, we can find that K for

nitrous acid 4.5 × 10-4. Using this value, we can readily determine K b for
NO2-
120
Kb =1.0 × 10-14 ÷ 4.5 × 10-4 = 2.2 × 10-11
NB:
1. The stronger the acid is, the larger its Ka, and the weaker its
conjugate base, the smaller its Kb. Likewise, the weaker the acid
(the smaller the Ka), the stronger the conjugate base (the
larger the Kb)·
2. Anions derived from strong acids, such as Cl- from HCl, do not react
with water to affect the pH. Nor do Br -, I-, N03-, S042-, and Cl04- affect
the pH, for the same reason. They are spectator ions in the acid-base
sense and can be described as neutral ions. Similarly, cations from
strong bases, such as Na+ from NaOH or K+ from KOH, do not react
with water to affect the pH. Hydrolysis of an ion occurs only when it
can form a molecule or ion that is a weak electrolyte in the reaction
with water. Strong acids and bases do not exist as molecules in dilute
water solutions.
EXAMPLE
What is the pH of a 0.10 M NaClO solution if Ka for HClO is 3.0 x 10-8?
SOLUTION:
The salt NaClO exists as Na+ and ClO-. The Na+ ions are spectator ions, but
ClO- ions undergo hydrolysis to form the weak acid HClO.
Let x equal the equilibrium concentration of HClO (and OH-):
ClO-(aq) + H20(l) HClO(aq) + OH-(aq)
(0.10 - x) M xM xM
The value of Kb for the reaction is (1.0 x 10-14)/(3.0 x 10-8) = 3.3 x 10-7.
121
Because Kb is so small, we can neglect x in comparison with 0.10 and thus
0.10 - x ≈ 0.10.
NB;
Anions with ionizable protons such as HC03 - , H2P04 - , and HP042-may be
either acidic or basic, depending on the relative values of Ka and Kb for the
ion
Acidic Salts
Cations that are derived from weak bases react with water to increase the
hydrogen ion concentration; they form acidic solutions. The ammonium ion
is derived from the weak base NH3 and reacts with water as follows:
This reaction is completely analogous to the dissociation of any other weak

acid, such as acetic acid or nitrous acid. We can represent this dissociation of
ammonium ion more simply:
Here too, the acid-dissociation constant is related to the Kb of NH 3, which is

the conjugate base of NH4+
122
Knowing the value of Kb for NH 3, we can calculate the acid dissociation
constant from equation [3];
Kw
Ka=
Kb
[3]
Cations of alkali metals (Group 1A) and the larger alkaline earth ions, Ca 2+,
Sr2+ and Ba2+, does not react with water because they come from strong
bases. Thus, these ions have no influence on the pH of aqueous solutions.
They are merely spectator ions in the acid-base reactions. Consequently,
they are described as being neutral in the acid-base sense. The cations of
most other metals do not hydrolyze to produce acidic solutions. Metal
cations are coordinated with water molecules, and it is the hydrated ion that
serves as the protonated donor. The following equation illustrates this
behavior for hexaaqua iron (iii) ion
We frequently omit the coordinated water molecules from such

equations. For example, Equation [4] may be written as
[5]
7.10 Solubility and solubility products

In this section we are going to consider the solubility of ionic solids in water.
“Solubility” may be considered to be an equilibrium; the equilibrium is

between solid and ions in solution.
Any ionic solid is 100% ionized in aqueous solution; once it actually

dissolves.
123
The term solubility always refers to the amount of solid (either in moles or
grams) that actually does dissolve in solution, producing ions; this amount
can be calculated for a particular solid.
The term solubility may also be used in a qualitative sense; there is no

“magic point” above which a salt can be described as “soluble”, and below
which a salt can be described as “insoluble”
Note that;
“Soluble” - at least 0.1 mol L-1 dissolves
“Slightly Soluble” - roughly 0.001 to 0.1 mol L-1
“Insoluble” - less than 0.001 mol L-1
Example 1
What is the form of equilibrium constant for this equation?
Bi2S3(s) 2 Bi3+(aq) + 3 S2-(aq)
Solution
K = [Bi3+]2 [S2-]3
Example 2
For a solution of AgCl in water, the equilibrium is: AgCl(s) Ag+

(aq) + Cl-(aq)
When the equilibrium is set up all three components must be present, to be

sure that the system is at equilibrium.
The equilibrium constant, K = [Ag+] [Cl-]
We call this type of Ka Solubility Product Constant, symbolized by Ksp.
124
So, Ksp (AgCl) is the solubility product constant for AgCl, when it dissolves
(or tries to) according to the above equation. Like most equilibrium
constants (Keq’s), its value depends on temperature, T; this is why more
solids usually dissolves in a solution at a higher temperature.
Example 3
Calculate the solubility, in mol L-1, of AgCl(s). [Ksp (AgCl) = 1.8 × 10-10]
Solution
Ksp = [Ag+] [Cl-]
1.8 × 10-10 = s × s
= s2
s = 1.34 × 10-5 MolL-1
N/B: To use Ksp, s must be in MolL-1
7.11 Buffer Solutions

A buffer solution is one which maintains its pH fairly constant even upon the
addition of small amounts of acid or base.
In other words, a buffer solution resists (or buffers) a change in its pH. That
is, we can add a small amount of an acid or base to a buffer solution and the
pH will change very little. Buffer solutions usually consist of a mixture of a
weak acid and its salt with a strong base e.g., CH 3COOH and CH3COONa, or
that of a weak base and its salt with a strong acid e.g., NH 4OH and NH4Cl.
125
The solution of any salt of a weak acid and a weak base e.g., ammonium
acetate, also shows buffering property
There are two types of buffers, acid buffer and basic buffer;
Acid buffer: A buffer solution containing large amounts of a weak acid, and
its salt with a strong base, is termed as an acid buffer. Such buffer solutions
have pH on the acidic side i.e., pH is less than 7 at 298 K. The pH of an acid
buffer is given by the equation e.g.: CH3COOH and CH3COONa
Basic buffer: A buffer solution containing relatively large amounts of a

weak base and its salt with a strong acid is termed as a basic buffer. Such
buffers have pH on the alkaline side i.e., pH is higher than 7 at 298 K. e.g.:
NH4OH and NH4Cl
Let's examine how a buffer works. Consider a buffer composed of a

hypothetical weak acid HX and one of its salts MX, where M+ could be
Na+, K+, or other cations. The acid-dissociation equilibrium in this
buffer involves both the acid, HX, and its conjugate base X-
The corresponding acid-dissociation-constant expression is;
Solving this expression for [H+], we have
We see from this expression that the hydrogen-ion concentration and

therefore the pH is determined by two factors: the value of Ka for the weak
126
acid component of the buffer, and the ratios of the concentrations of the
weak acid and its conjugate base, [HX]/[X-].
If OH- ions are added to the buffered solution, they react with the acid
component of the buffer:
This reaction results in a slight decrease in the [HX] and a slight increase
in the [X-], as long as the amounts of HX and X- in the buffer are large
compared to the amount of the added OH-. In that case, the ratio
[HX]/[X-] doesn't change much, and thus the change in the pH is small. If
H+ ions are added to the buffered solution, they react with the base
component of the buffer:
This reaction causes a slight decrease in the [X-] and a slight increase in
the [HX]. Once again, as long as the change in the ratio [HX]/[X-] is small,
the change in the pH will be small. Buffers resist changes in pH most
effectively when the concentrations of the conjugate acid-base pair, HX
and X-, are about the same. We see from examining Equation
that under these conditions their ratio is close to one, and thus the [H+]
is approximately equal to Ka· For this reason we try to select a buffer
whose acid form has a pKa close to the desired pH.
Because we are interested in pH, let's take the negative
logarithm of both sides of Equation and

obtain;
127
Because -log[H+] = pH and -log[Ka] = pKa, we have
and making use of the properties of logarithms we have
In general;
Topic Summary
 A reaction is reversible when reactants can react to form products, and

products can react to form the reactants again.
 A reaction is in chemical equilibrium when the rate of the forward
reaction equals the rate of the reverse reaction.
 In an open system, energy and matter can enter and leave the
system. In a closed system energy can enter and leave the system,
but matter cannot.
 The equilibrium constant (Kc) relates to the concentration of the
reactants and products at equilibrium, and can be calculated using the
following expression:
128
where aA+bB ⇌ cC+dD
A and B are reactants, C and D are products and a, b, c, and d are the
coefficients of the respective reactants and products.
 A high Kc value means that the concentration of products at

equilibrium is high and the reaction has a high yield of the products. A
low Kc value means that the concentration of products at equilibrium is
low and the reaction has a low yield of the products.
 Le Chatelier's Principle states that if an external stress (change in
pressure, temperature or concentration) is applied to a system in
chemical equilibrium, the equilibrium will change in such a way as to
reduce the effect of the stress.
 Although a change in temperature, concentration or total pressure will
affect the equilibrium position, only temperature will affect the
equilibrium constant Kc.
 The principles of equilibrium are very important in industrial

applications such as the Haber process, so that productivity can be
maximized.
Whether a solution of a salt will be acidic, neutral, or basic can be

predicted on the basis of the strengths of the acid and base
from which the salt was formed.
1. Salt of a strong acid and a strong base: Examples: NaCl, KBr,

and Ba(N03)2. Neither the cation nor the anion hydrolyzes, and the
solution has a pH of 7.
129
2. Salt of a strong acid and a weak base: Examples: NH 4Br,
ZnC12, and Al(N03)3. The cation hydrolyzes, forming H + ions, and
the solution has a pH less than 7.
3. Salt of a weak acid and a strong base: Examples: NaN0 2, KC2H302,
and Ca(OCl)2. The anion hydrolyzes, forming OH- ions, and the
solution has a pH greater than 7.
4. Salt of a weak acid and a weak base: Examples: NH 4F, NH4C2H302,
and
5. Zn(N02)2. Both ions hydrolyze. The pH of the solution is determined
by the relative extent to which each ion hydrolyzes.

1. Arun Bahl: Essentials of Physical Chemistry, Multicolor
Edition

1. Define Bronsted-Lowry acids and bases.
2. Which of the following ions will react with water in a hydrolysis reaction:
Na+, Ca2+, Cu2+, Zn2+, F-, SO32-, Br-?
3. For those ions in question 2 that undergo hydrolysis, write net ionic
equations for the hydrolysis reaction.
4. The Ka for HCN is 4.9 x 10-10. What is the value of Kb for CN-?
5. What are the conjugate base and conjugate acid of H2P04-?
6. From what acid and what base were the following salts made: CaS0 4,
NH4Br, and BaCl2?
130
7. Define the term salt.
8. Tell whether 0.1 M solutions of the following salts would be acidic, neutral,
or basic: BaC12, CuS04, (NH4)2S04, ZnC12, NaCN.
9. If the pH of a solution is 8, what are the hydrogen-and hydroxide-ion

concentrations?
10. The pH of a 0.1 M MCI (M + is an unknown cation) was found to be 4.7.

Write a net ionic equation for the hydrolysis of M + and its corresponding
equilibrium expression Kb. Calculate the value of Kb.
11. What is the pH of a solution that is 0.10 M HC 2H302 and 0.20 M

NaC2H302? Ka for acetic acid 1.8 X 10-5
12. The equilibrium constants for the reaction
is 60 at 400 ˚C. Calculate the number of moles of hydrogen iodide in

equilibrium with 2 moles of hydrogen and 0.3 moles of iodine. (Ans = 6.0
moles).
7.14 Activity
Students to attempt the review questions in section 7.13.
131
TOPIC EIGHT: ELECTROCHEMISTRY
Topic Introduction
In this topic we will examine electricity in chemistry. Reactant chemicals

which can be able to undergo reduction oxidation reactions. Spontaneous
reactions will be related to the construction of simple galvanic cells. Your
torch battery or your simple mobile battery is simple galvanic cell utilizing
some chemicals.
Learning Outcomes
By the end of this topic, you should be able to:
 Define the term electrochemistry

 Express simple spontaneous reactions in the ionic form
 Express an ionic reaction in two partial reactions
 Balance simple redox reactions
 Identify the oxidation at anode and the reduction at the cathode as
partial reactions
 Discuss the construction of simple Galvanic cells
 Write cell reactions for simple galvanic cells
 Perform simple calculations to determine the cell e.m.f, E0 for simple
galvanic cells
Topic times
8.0 Electrochemistry
Electrochemistry is the branch of physical chemistry that deals with the
conversion of chemical energy in to electrical energy and vice versa.
132
8.1 Spontaneous reduction-oxidation (redox) reactions
In the reaction between sodium and chlorine to give sodium chloride
2 Na(S )+ 2Cl( g) → 2¿ ¿ ¿
+¿¿
Na(s) gives up electrons to become Na and Cl gains electrons to become
−¿¿
Cl .
We therefore imagine that the reaction takes place in two steps called half-
reactions
−¿ ¿
Na❑ → Na+¿+e ¿
(A)
−¿¿
Cl+ e
−¿→ Cl ¿
(B)
But rarely does a Cl molecule exist alone but two rather combine forming Cl
−¿¿
−¿ →2 Cl ¿
Cl 2+2 e
Since in a balanced reaction electrons don’t appear, we multiply equation (A)

by 2 and add it to equation (B)
The overall reaction is an electron transfer reaction; electrons are

transferred from sodium to chlorine. Electrons transfer reactions are
commonly called oxidation-reduction reactions or redox reactions. Any
reaction in which an electron or electrons are lost for example reaction (A) is
called the oxidation. Reduction reaction is the one in which electrons are
gained for example equation (B).
Worked examples
133
For the reaction
4 Na(s )+O2 (g) → 2 Na2 O(s)
a) Write the oxidation reaction

−¿¿
+¿+e ¿
Na→ Na
b) Write the reduction reaction
−¿¿
O2 +4 e → 2O
2−¿¿
c) Combine the two half reactions

−¿¿
Na→ Na
+¿+e ¿
(A)
−¿¿
O2 +4 e → 2O
2−¿¿
(B)
NB: To cancel out electrons, equation A is multiplied by 4 and added to B
8.2 Construction of Galvanic Cells

Variously referred to as electrochemical cell or Voltaic cell.
A galvanic cell is a device that uses a spontaneous chemical reaction to

produce an electric current. For example if we place a piece of zinc in a
solution of copper(II) sulphate, the blue color of copper sulphate fades
because of the spontaneous reaction.
In ionic form
134
Separating in to two half-reactions;
When the reaction is carried out this way, the transfer of electrons occurs on
the surface of zinc and cannot be directly observed.
However, if the oxidation and reduction (REDOX) reactions are separated

from each other, the electron transfer can occur through an external circuit.
This can be achieved by connecting a piece of zinc, called zinc electrode
immersed in a solution of zinc sulphate to a piece of copper electrode
immersed in a solution of Copper(II) sulphate.
Before connecting the wire, there are two possible reactions.
But because zinc is more reactive than copper there will be more electrons
on the side of Zn than Cu side. And therefore when the system is connected
by a wire, electrons will flow from Zn to Cu as shown. Hence the two
reactions will be:
135
In the reduction reaction therefore the Cu comes from the solution and the
two electrons come from zinc. The positive charge ( Zn2+¿¿ left behind) and
2−¿ ¿
negative charge ( SO 4 left behind) cannot be sustained for long and
therefore the cells stop functioning within a short time.
To overcome this problem, the solutions are brought in to contact but not be
allowed to mix. This is done by use of a porous barrier or use of a salt
bridge.
Figure: The zinc–copper voltaic cell
The porous barrier allows sulphate ions to pass through and as they do so
they relieve the cathode of the negative charge. Once they go through they
react with Zn2+¿¿ and relieve the anode of the positive charge.
The salt bridge mainly consists of KCl, KNO3 or NH 4 Cl solution and like in the
cause of porous barrier relieves both compacts of the charge by slowly
mixing with the cation and anion of salt bridge.
Exe
136
Write the net ionic equation for the reaction that will occur when a silver bar
in a solution of AgNO3 is suitably connected to a copper bar in a solution of
CuSO4
8.3 Electrode Potential

The electrode surface may acquire net positive or negative charge depending
on whether the rate of deposition or dissolution predominates. In either case
a charge separation results across the metal-solution interface.
The potential difference that exists across the metal-solution interface is

known as electrode potential.
For a given electrode the potential depends on;
 Concentration of ions in solution-the higher the concentrations, the

higher the chances of attacking the electrodes.
 Temperature of the system
 Partial pressure for each component if gaseous systems are involved
8.3.1 Electromotive Force (e.m.f)

The difference in potential between the electrodes e.g. Zn/Cu that causes a
current to flow is due to the fact that Zn has a greater tendency to give up
electrons than copper.
This means that electrons will flow from area of higher oxidation potential
(Zn) to the one of low oxidation potential (Cu).
The potential difference that causes a flow of current from the electrode of
higher oxidation potential to one of lower oxidation potential is known as the
electromotive force, e.m.f of the cell.
137
8.3.2 Half-Cell Potential
It is impossible to measure the e.m.f of half-cell potential without a second
electrode since no current flows in an incomplete circuit. Normally we use
standard hydrogen electrode at 1 atmosphere pressure, 25 ℃ and 1M
solution.
Figure: The standard hydrogen electrode (SHE).
Conventionally the standard hydrogen electrode is assigned a value

E =O. OOOV meaning any measured potential is attributed to the other
0
electrode.
Standard half-cell potentials can be combined into standard cell potentials,

also symbolized E0 . The superscript 0 denotes the standard state of the
system, which means that the following conditions exist in the cell:
 Any solids and liquids are pure substances.

 Any solutes are 1.000 M.
 Any gases are at 1.000 atm pressure.
Traditionally, the half-cell, cell potentials are given as reduction potentials

−¿→Zn ¿ −¿¿
¿
( Zn2+¿+2 e . However, oxidation potential of the same half-cell ( Zn→ Zn 2+¿+2 e
¿
) will have the same value but opposite in sign standard reduction potentials.
138
The more positive value of the E0 , the more easily the reduction. For
−¿→Zn ¿
example, it is harder to reduce zinc, Zn2+¿+2 e ¿

than reducing cadmium,
in comparison to the reduction of H +¿¿ .
−¿→Cd ¿
¿
Cd 2+¿+2 e
8.4 Cell notation

Consider the cell reaction;
The cell is denoted as:

2+¿/ Cu( s) ¿
2+¿ /¿Cu( aq) ¿
Zn(s ) /Zn(aq)
139
L.H.S- gives the anode
R.H.S- gives the cathode
/- indicates different phases
//- indicates a salt bridge
Worked example
1. for the cell

2 +¿/Cu (s ) ¿
2+¿/ ¿Cu(aq ) ¿
Cd(s) /Cd (aq )
a) Write the anode reaction

b) Write the cathode reaction
c) Write the overall cell reaction
d) Calculate the E0
Solution
−¿ ¿
a) Anode reaction; Cd → Cd2 +¿+ 2e ¿
−¿→ Cu¿
b) Cathode reaction; Cu2+¿+2 e ¿
c) Overall cell reaction; a + b
0
d) ECell =Ea + E b= 0.403 + 0.3419= 0.7449V
2. For the cell reaction:
Write the;
a) Anode reaction
b) Cathode reaction
c) Cell notation
140
Solution
−¿¿
¿
a) Al → Al 3+¿+3 e
−¿→ Cu¿
b) Cu2+¿+2 e ¿
2+ ¿/Cu (s )¿
3 +¿/ ¿Cu(aq) ¿
c) Al(s) / Al(aq)
Topic Summary
 Electrochemistry is the study of electricity in chemistry.

 Redox is reaction in which both reduction and oxidation process take
place simultaneously.
 A galvanic cell is a simple device able to utilize a spontaneous redox
reaction to produce an electric current.
 Electrode potential is the potential charge causing a charge separation
between the metal and the solution interface.
 Electromotive force (e.m.f) is the actual driving force that causes the
electrons to flow from one electrode to the other.
 Half-cell potentials give the driving force of an electric current on the
hydrogen scale.
 The cell notation indicates that anode and cathode, separation
between any two phases as well as the existence of a liquid junction.
.5 Further Reading/ References
1. Goldberg, D. E. (2006). Fundamentals of chemistry. McGraw-
Hill.
2. Toon, E. R., Ellis, G. L., & Brodkin, J. (1968). Foundations of
chemistry.
3. Gammon, S. D., & Ebbing, D. (2006). General chemistry.
Cengage Learning.
141
1. Iron dissolves in dilute acid to give
2+ ¿+ H 2(g) ¿
+¿+Fe( s) → Fe(aq) ¿
2 H(aq)
The potential of a cell constructed from a standard hydrogen electrode

and half-cell consisting of an iron electrode in a 1M solution of FeSO 4 is
0.44V. What is the standard reduction potential of the Fe half-cell.
(Ans= -0.44V)
2. The standard cell potential for the cell
Zn(s ) / ZnSO 4 (aq) / ¿ AgNO 3(aq) / Ag( s) is 1.56V, if E0 =−0.76 V , what is the standard
reduction potential for the half-reaction

−¿→ Ag( s ) ¿
Ag+¿+e (Ans= -0.8V)

¿
3. Why do copper, silver and gold occur naturally in their metallic states
whereas potassium, magnesium and aluminum do not?
4. Describe by appropriate chemical equations, the corrosion that occurs
when copper and steel hot-water pipe are connected.
5. Compare the standard potential for the following reaction.
❑ 3+ ¿¿
2+ ¿→3 Cu( s)+2 Cr (aq) ¿
2 Cr (s )+3 Cu(aq)
You are given; ECu =0.34 V ¿ and ECr =−0.74 V ¿ (Ans = -1.08V)
¿ ¿
8.7 Activity
Students should attempt and discuss the questions in section 8.6
142
TOPIC NINE: THERMOCHEMISTRY
Topic Introduction
In this topic heat change involved in chemical reactions will be studied. This
includes heats of reaction and heats of formation. Hess’s law will be
discussed.
Learning Outcomes
At the end of the topic you should be able to:
 Define the terms; thermochemistry, enthalpy change of a reaction and

enthalpy of formation
 Differentiate between enthalpy; at a constant pressure and constant
volume
 Perform simple calculations involving ∆ E and ∆ H
 Explain the factors that determine the magnitude of ∆ H
0
 Perform simple calculations to calculate ∆ H 0 and ∆ H f
 State and explain Hess’s law
Topic times
9.0 Thermochemistry
Is the branch of physical chemistry that deals with the heat changes that
normally accompanies physical and chemical changes.
Since the energy change in chemical reactions are generally due to breaking
up of the existing bonds between the atoms and the formation of new
bonds. Thermochemistry should therefore provide important information
regarding the bond energy changes.
143
9.1 Enthalpy of a Reaction, ∆ H
Is the amount of heat absorbed or evolved in the transformation of the
reactants to the products at the same temperature and pressure e.g.
1
H 2 ( g) + O2(g ) → H 2 O (l) ∆ H =−285.83 kJ . mol−1
2
Where
A negative sign indicates heat is evolved
A positive sign indicates heat is absorbed
• Potential energy is a type of energy resulting from the attraction or

repulsion between different particles:
- particles which repel each other have a positive potential energy
- as repelling particles are forced closer together, their potential energy
increases
- as repelling particles move further apart, their potential energy
decreases until they are an infinite distance apart and they have zero
potential energy
- particles which are attracted to each other have a negative potential
energy
- as attracting particles get closer together, their potential energy
becomes more negative (ie it decreases)
- as attracting particles are pulled further apart, their potential energy
becomes less negative (ie it increases) until they are pulled an infinite
distance apart and they have zero potential energy
• All chemical substances are held together by the attraction between
protons and electrons; all chemical substances therefore have a negative
potential energy (called chemical potential energy); the stronger the
attractive forces holding the substance together, the more negative (ie the
lower) the potential energy of the substance and the more stable it is
144
• Chemical potential energy is also known as enthalpy and is given the
symbol H
• When a chemical reaction takes place, the products and reactants have
different enthalpies and thus there is a change in enthalpy; but since total
energy is always conserved, any change in enthalpy must be balanced by
an equal and opposite change in kinetic, or heat energy; the change in
enthalpy during a chemical reaction is shown by the symbol ΔH.
9.1.1 Factors determining the magnitude of ∆ H

-Whether the reaction was carried out at a constant volume or
pressure
-Temperature of the reaction
-State of aggregation of the reactants i.e. whether solids, liquids, or

gases. If solids, whether powdered or not.
9.2 Exothermic and Endothermic Reactions

• In some reactions, the products are more stable than the reactants; the
products therefore have a lower enthalpy than the reactants, and the
enthalpy decreases; this can be shown in an enthalpy level diagram:
•In these reactions there is a negative enthalpy change (ΔH = -ve); since
the total energy is always conserved, the heat energy of the species must
145
increase by an equal amount; the surrounding temperature therefore
increases.
• In these reactions, there is a transfer of energy from chemical potential
energy to heat energy and an increase in temperature; such reactions give
out heat and are said to be EXOTHERMIC
• In practice, not all of the energy will be transferred into heat (kinetic)
energy; in some cases, sound energy will be produced as well; it is also
possible in some cases to produce electrical energy rather than heat energy;
but the loss in chemical potential energy will always be equal to the total
gain in heat, kinetic, electrical or sound energy.
In other reactions, the reactants are more stable than the products; the
products therefore have a higher enthalpy than the reactants, and the
enthalpy increases; this can be shown in an enthalpy level diagram:
• In these reactions there is a positive enthalpy change. (ΔH = +ve); since

the total energy is always conserved, the heat energy of the species must
decrease by an equal amount; the surrounding temperature therefore
decreases
• In these reactions, there is a transfer of energy from heat energy to
chemical potential energy and a decrease in temperature; such reactions
absorb heat and are said to be ENDOTHERMIC
146
9.3 Molar Enthalpy Changes
• The quantity of heat energy absorbed or given out during a chemical
reaction (q) depends on the amount of substance used; it is therefore
necessary to specify the amount of reactants used when recording energy
changes
• Enthalpy changes are generally measured per mole of reacting substance
and typically have units of kJmol -1; this is known as the molar enthalpy
change of a reaction; for example, in the reaction, A + 3B → 2C + 4D, the
-1
molar enthalpy change for this reaction, in kJmol , is taken to be the
enthalpy change when one mole of A reacts with three moles of B
• Heat change and molar enthalpy change can be interconverted using the
following equation
9.3.1 Practical measurement of enthalpy changes

• Enthalpy changes are generally measured by carrying out a reaction under
controlled conditions in a laboratory and measuring the temperature change;
the amount of heat required to change the temperature of a system by 1K
(or 1oC) is known as the heat capacity of a system (H c); it is measured in
JK-1
• The heat energy change (q) for a given reaction can therefore be
calculated from the temperature change (ΔT) from the equation, if the heat
capacity of the system is known:
• The specific heat capacity (c) is the amount of heat required to heat 1 g
of a substance by 1 K (or 1oC)
- therefore Hc = c x m and q = m x c x ΔT
147
- most enthalpy change experiments carried out in the laboratory either take
place in aqueous solution or are used to heat a container containing water; it
is therefore the water which is being heated or cooled; the specific heat
capacity of water is known to be 4.18 JK-1g-1; this value can be used for any
aqueous solution.
- the mass of water can be calculated from its volume and its density; the
-3
density of water is 1gcm so its mass in grams is equal to its volume in cm3
9.3.2 Definitions of special enthalpy changes

The enthalpy changes of some reactions are frequently used in chemistry
and so have been given special names:
• The enthalpy of formation of a substance is the enthalpy change
when one mole of that substance is formed from the most stable
allotropes of its elements in their standard states; its symbol is ΔH of
Eg C(s) + 2H2(g) → CH4(g), ΔH = -74.8 kJmol -1; the enthalpy of formation

-1
of methane is -74.8 kJmol
Eg H2(g) + 1/2O2(g) → H 2O(l), ΔH = -285.8 kJmol -1; the enthalpy of

-1
formation of water is -285.8 kJmol
- the standard enthalpy of formation of all elements in their standard
states is zero
- it is often not possible to measure enthalpies of formation directly
- formation reactions can be exothermic or endothermic so enthalpies of
formation can have negative or positive values
• The enthalpy of combustion of a substance is the enthalpy change
148
when one mole of that substance is burned in an excess of oxygen
Eg H 2(g) + 1/2O2(g) → H 2O(l), ΔH = -285.8 kJmol -1; the enthalpy of
combustion of hydrogen is -285.8 kJmol -1
Eg CH 4(g) + 2O2(g) → CO2(g) + 2H 2O(l), ΔH = -890.3 kJmol -1; the

enthalpy of combustion of methane is -890.3 kJmol -1
- burning a substance in oxygen is almost always exothermic, so standard

enthalpies of combustion almost always have negative values
- substances which do not support combustion, like water, carbon dioxide
and most other oxides, have zero enthalpy of combustion
- most enthalpies of combustion can be measured directly
• The enthalpy of neutralisation of an acid and a base is the enthalpy
change when one mole of water is formed by the reaction of that
acid with that base
Eg HCl(aq) + NaOH(aq) → NaCl(aq) + H 2O(l), ΔH = -57.3 kJmol-1; the
enthalpy of neutralisation of HCl by NaOH is -57.3 kJmol-1
- it is usually possible to measure enthalpies of neutralisation directly
• The enthalpy of solution of a substance is the enthalpy change when
one mole of that substance dissolves in an excess of water:
Eg NaOH(s) → Na +(aq) + OH -(aq), ΔH = -44.5 kJmol -1; the enthalpy of
-1
solution of NaOH is -57.3 kJmol
- it is possible to measure enthalpies of solution directly if the substance is
soluble in water
0
Table showing ∆ H f of some common substances
149
The enthalpy of formation of a compound is equal to the enthalpy constant
of the compound is related to its stability.
⟹ A positive value means the compound is less stable than its elements
while negative value means the compound is more stable than its elements.
Worked example
Use the table above to determine the enthalpy of the reaction
SO3(g )+ H 2 O(l ) → H 2 SO4 (l )
0
0 0
∆ H reaction =∆ H products −∆ H reactants = ∆ H H 2
SO4 −∆ H 0H O −∆ H 0SO
2 ❑ 3
= -814.0- ((-285.8) + (-395.7))= -132.5kJ/mol
Exercise
Use the table given to determine the enthalpy of the formation of the
reaction below;
4 NH 3 (g) +5 O2( g) → 4 NO2 (g) + H 2 O(g ) Ans= -904.8
9.4 Hess’s law of constant heat summation
The total enthalpy change for the reaction is the same whether the reaction
takes place in a single step or in several steps.
150
For example
Standard enthalpy of formation of methane (CH4)
C ( graphite ) +2 H 2 (g) CH4(g)
The reaction does not take place as written, so we use Hess’s law. To begin,
the following reactions involving C, H2 and CH4 with O2 have all been studied
θ
and the ∆ H rxn values accurately determined.
θ
a) C(graphite) + O2 (g) CO2(g) ∆ H rxn = -393.5 kJ
θ
b) 2H2 (g) + 02 2H2O (L) ∆ H rxn = -571.6 kJ
θ
c) CH4(g) + 2O2(g) CO2(g) + 2H2O ∆ H rxn = -890.4 kJ
Because we want to obtain one equation containing only C and H 2 as

reactants and CH4 as products, we must reverse (c ) to get
θ
d. CO2(g) + 2H2O CH4(g) + 2O2 ∆ H rxn =890.4 kJ
The next step is to add equations a, b and d
θ
C(graphite) + O2 (g) CO2(g) ∆ H rxn = -393.5 kJ
θ
2H2 (g) + 02 2H2O (L) ∆ H rxn = -571.6 kJ
θ
CO2(g) + 2H2O CH4(g) + 2O2 ∆ H rxn =890.4 kJ
151
θ
C(graphite) + 2H2O (g) CH4(g) ∆ H rxn = -74.7 kJ
Thus;
The enthalpy depends on the initial and the final states of the reacting
system and is independent of the path connecting them.
Hess’s law enables us to treat chemical equations just like algebraic

equations in mathematics.
Topic Summary
Thermochemistry deals with heat changes in chemical reactions.
q v =∆ E
∆ H =∆ E+ RT ∆ n
Pressure, temperature and state of aggregation affect the magnitude of ∆ H .
Standard enthalpies, ∆ H , are measured at 1 atm and 298K.
Standard enthalpies of elements in their pure form are assigned a value of

zero.
By Hess’s law, only the initial and final products are important means of
achieving the two states don’t affect the value of ∆ H 0.

1. Goldberg, D. E. (2006). Fundamentals of chemistry. McGraw-Hill.
2. Toon, E. R., Ellis, G. L., & Brodkin, J. (1968). Foundations of
chemistry.
3. Gammon, S. D., & Ebbing, D. (2006). General chemistry. Cengage
Learning.
152
1. From the following equations and enthalpy changes
θ
C(s) + O2(g) CO2(g) ∆ H rxn = -393.5 kJ
1 θ
H2(g) + O H20 ∆ H rxn = -285.8kJ
2 2(g)
θ
2C2H2(g) + 5O2(g) 4C02(g) + 2H2O ∆ H rxn = -2598.8 kJ
Calculate the enthalpy formation of C2H2 from its elements 2C(s) + H2(g)
C2H2(g)
θ
4C02(g) + 2H2O(l) 2C2H2(g) + 5O2(g)∆ H rxn = +2598.8kJ
θ
4C(s) + 4O2(g) 4CO2(g) ∆ H rxn = -1574.01 kJ
θ
2H2(g) + O2(g) 2H20 ∆ H rxn = -571.6 kJ
θ
4C(s) + 2H2(g) 2C2H2(g) ∆ H rxn = +453.2kJ
θ
2C(s) + H2(g) C2H2(g) ∆ H rxn = +226.6kJ
2. For the reaction
3 H 2(g ) + N 2(g ) → 2 NH 3 (l ), ∆ E at 1000K is -608.7kJ/mol. Given R= 8.314 j . K .mol−1,
determine the ∆ H . (Ans= -625.3 j . mol−1)
9.7 Activity
Students to attempt questions in section 9.6
153

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EGERTON UNIVERSITY

CHEM 130: GENERAL INORGANIC AND PHYSICAL CHEMISTRY

Credit Factor: 3.0 (Lectures 30 Hrs. Practicals 30 Hrs.)

Introduction to the course

This course will introduce you to general concepts of inorganic and

1.1 Dalton’s atomic theory..............................................................7

1.1.1 Postulates of Dalton’s atomic theory..........................................7

1.1.2 Limitations/drawbacks of Dalton’s atomic theory.........................7

1.2 The fundamental components of atoms........................................7

1.2.1 Atomic Number (Z).................................................................8

1.2.2 Mass number (A)....................................................................8

1.3 Relative Atomic Mass................................................................9

1.4 Review of Atomic Structure.....................................................10

1.4.1 Rutherford’s atomic model.....................................................10

1.5 Further Reading/References...................................................13

1.6 Review Questions...................................................................13

TOPIC TWO: STOICHIOMETRY & CHEMICAL CALCULATIONS...........15

2.1 Avogadro’s Number & The Mole Concept.................................16

2.2 Determining the Formula of a Compound................................17

2.2.1 Percent Composition.........................................................17

2.2.2 Empirical and Molecular Formula.......................................18

2.3 Ways of Expressing Concentrations of Solutions.....................20

2.3.1 Percent Concentration;..........................................................20

2.3.2 Concentration by mass; ppm & ppb.........................................21

2.3.4 Molality (m).........................................................................22

2.4 Stoichiometric Calculations: Amounts of Reactants and

2.4.1 Calculations involving a limiting reagent...................................26

2.4.2 Calculating the Percentage Yield..............................................28

2.5 Further Reading/References...................................................30

2.6 Review Questions...................................................................31

CHAPTER THREE: MODERN PERIODIC TABLE...................................32

3.1 Electronic Structure................................................................32

3.1.1 Quantum Numbers................................................................32

3.1.2 Atomic Orbitals.....................................................................33

3.2 Relationship between Quantum Numbers and atomic orbitals 34

3.3 Writing Electron Configurations..............................................34

3.3.1 Pauli Exclusion Principle.........................................................35

3.3.2 Hund’s Rule..........................................................................35

3.3.3 Aufbau Principle....................................................................36

3.4 Properties of Monatomic Ions.................................................38

3.4.1 Shielding effect.................................................................39

3.5 Evidence for Electronic Structure of atoms..............................40

3.5.1 Using Ionisation energies to predict electronic structure -evidence

3.6.1 Development of the Periodic Table...........................................41

3.6.2 Modern Periodic Table.......................................................42

3.6.3 Periodic Classification of Elements...........................................44

3.6.4 Electronic configuration in relation to periodic table...................44

3.7 General Trends in Physical and Chemical Properties in Period 3,

3.7.1 Atomic Size (Atomic Radius)................................................45

3.7.2 Moving Across a Period..........................................................45

3.7.3 Moving Down a Group............................................................45

3.7.4 Cations and Anions................................................................45

3.7.5 Ionization Energy and Electron Affinity.....................................46

3.8 Further Reading/References...................................................49

3.9 Review Questions...................................................................49

CHAPTER FOUR: CHEMICAL BONDING.............................................51

4.1 Chemical Bond........................................................................52

4.2 Lewis Symbols & Structures....................................................52

4.3 Ionic Bond..............................................................................56

4.3.2 Factors Governing the Formation of Ionic Bonds........................57

4.3.3 Properties of Ionic compounds................................................58

4.4 Covalent Bond.........................................................................59

4.4.5 Intermolecular Forces in Covalent Compounds..........................62