ii

REFERENCES
Some Useful References and Recommended Reading:
1 Petrucci R. H. and Harwood W. S., “General Chemistry: Principles and Modern
Applications”. 7th edition. Prentice Hall. New Jersey.
2 McMarry J. and Fay R. C., “Chemstry”. Prentice Hall. New Jersey.
3 Hill G. C. and Holman J. S., “Chemistry in Context” 4th edition 1995, Thomas Nelson
and Sons Ltd Surry UK
4 General Chemistry: The Essential Concepts by Raymond Chang and Kenneth
Goldsby, 2013
5 Introductory Chemistry: A Foundation by Steven S. Zumdahl and Donald J. DeCoste,
2010
6 General Chemistry: Principles and Modern Applications (10th Edition) by Ralph H.
Petrucci, F. Geoffrey Herring, Jeffry D. Madura and Carey Bissonnette, 2010
7 General Chemistry by Darrell Ebbing and Steven D. Gammon, 2012
8 Chemistry: The Central Science (12th Edition) by Theodore E. Brown, H. Eugene H
LeMay, Bruce E. Bursten and Catherine Murphy, 2011
9 Any other college inorganic chemistry text book.
10 Internet Search

iii
 Lecture 1

1.0 Atomic Structure:

1 Lecture 1 Objectives or Aims

At the end of this unit you should be able to;

(a) describe the historical development of atomic structure
(b) describe the nature of electrons, protons and neutrons
(c) explain the Thomson model
(d) describe the nature of electromagnetic radiation
(c) explain Rutherford model
(d) discuss the Bohr model and hydrogen spectrum

1.0 Introduction

This lecture describes the historical development of the classical view of atomic structure. It
starts with earlier view of atoms and how the understanding of atom developed. In this
lecture we will learn different classical views that were put forward in history, their success
and failures.

A century ago, scientists believed that atoms were solid indestructible particles like minute
rebounding balls. Since then, they have built up a great deal of evidence concerning the
detailed structure of atoms.

Experiments involving electrolysis suggested that certain compounds contained charged

particles called ions. The formation of these ions from atoms could be explained by the loss
or gain of negatively charged particles (electrons). This led to the idea that atoms consisted
of a small positive charged nucleus surrounded by negative electrons. Later, scientists

1
discovered that the nucleus is composed of two kinds of particles-protons and neutrons. In
this lecture, we shall consider historical development of theory of atomic structure.

SELF-TEST QUESTIONS

i) Define the words, atom, element and molecule.

ii) Write briefly on Dalton’s Atomic theory

1.1 Classical View of Atomic Structure

The classical view of atomic structure was constructed with the body of knowledge
accumulated in physics over several centuries preceding the 20th century. This body of
knowledge is called classical physics.

Known facts:
Through experience, physicists have identified a long list of particles which make up the
atoms. The most fundamental particles are:
1 Electrons
2 Protons
3 Neutrons

Electrons
Electrons were discovered by J. J. Thomson in 1897, when conducting experiment on
conductivity of electricity of gases at very low pressure. He initially called them cathode
rays.

The electron is negatively charged with a charge of -1.602189x10-19 C (Coulombs). For

convenience the charge of atomic and sub-atomic particles are described as multiple of this

2
value (also known as electronic charge). Thus the charge of electron is usually referred to as
-1.
The mass of electron me=9.109534x10-31 kg
=5.485x10-4 amu
1 atomic mass unit (amu) = 1.660565x10-27 kg

Symbol of electron is e-1.

Protons
Protons were discovered by J. J. Thomson, when later conducting experiment on conductivity
of electricity of gases at very low pressure. He initially called them positive rays

The protons has a charge of +1 electronic charge or +1.602189x10-19 C

The mass of proton mp=1.672648x10-27 kg
=1.007276 amu

Symbol p.

Neutrons
Neutrons were discovered by Chadwick in 1932. From his experiments he showed that
neutrons had almost the same mass as the protons. Chadwick was able to explain the
difficulty concerning the relative atomic masses of hydrogen and helium and later on the idea
of isotopes.

Neutrons have no charge. They are electrically neutral

The mass of neutron mn=1.674954x10-27 kg
=1.008665 amu

Symbol n.

3
Atomic Mass Unit
The mass of an atom is extremely small. The units of mass used to describe atomic particle is
the atomic mass unit or (amu). An atomic mass unit (amu) is equal =1.660565x10-27 kg or
=1.660565x10-24 g
Hence mass of proton=1.007276 amu
neutron=1.008665 amu
electron=5.485x10-4 amu

• From this comparison, we can see that the mass of proton and neutron are nearly
identical.
• The nucleus (protons plus neutrons) contain virtually all the mass of the atom.
• The electrons while equal and opposite in charge to the protons have only 0.005%
mass.

SELF-TEST QUESTIONS

The five main proposals in Dalton’s Atomic Theory of matter were:

1 All matter is composed of tiny indestructible particles called atoms.
2 Atoms cannot be created or destroyed.
3 Atoms of the same elements are alike in every way.
4 Atoms of different elements are different
5 Atoms can combine together in small numbers to form molecules.
a) In the light of modern knowledge about atoms, isotopes, molecules and atomic
structure comment on the truth of each of these proposals
b) Why is Dalton’s Atomic Theory still useful in spite of these limitations?

c) Describe the contributions of the following scientists to our knowledge of

atomic structure: John Dalton, J. J Thomson, R. A. Mullikan, James Chadwick
and Ernest Rutherford

4
 ACTIVITY
Visit the library the physics section, get a book on Atomic and Nuclear Physics and read on
classification of the elementary particles. You will be excited to learn of many particles , for
example: boson, fermions, leptons, mesons, baryons, photons, hyperons, nucleons, pions,
kaon, muon etc
NB/ You can get most of this information from internet.

1.2 Historical Development of Atomic Theory

The challenge was how these sub-atomic particles are arranged in an atom. Different atomic
models were proposed. The sections that follow describe some of the models that have been
proposed.

1.2.1 Thomson’s Plum Pudding or Raisin Bun Atomic Model (1856-

1940)

Thomson didn’t know exactly how positive electric charge was distributed in an atom, so he
considered the case that was easiest to describe mathematically. He developed a model in
which a positive charge is uniformly distributed in an electron imbedded sphere in such a
way that attraction of the positive charge just offsets the repulsion among the electrons. This
somehow resembles raising pudding.

5
 Figure 1.1. Thomson’s plum pudding or raisin bun atomic model

However, this model was discarded as more information on atomic structure was discovered.
Later on Rutherford proposed another Model.

1.2.2 Rutherford’s Nuclear Model of Atom (1871-1937)

Rutherford used α-particles (alpha particles), doubly ionized helium atom, He2+ to probe the
structure of matter. Based on Thomson’s model of the atom Rutherford expected that most α
particles would pass through atoms un-deflected. However, also he expected that any of the
positively charged α-particles that come close to an electron should be deflected to some
extent. By measuring such deflection he hoped to gain information about distribution of
electron in an atom. Rutherford assigned his assistant, Hans Geiger and an undergraduate
student Ernest Marsden an experiment to bombard a very thin foil of metal such as gold,
silver and platinum with α-partilces. They found that
i) Most of the particles went right through the foil undeflected
ii) A few particles were deflected sharply and once in a while α-particles would
bounce right back to the source.

6
 Figure 1.2 Angular Distribution of Rutherford Scattering

The deflection and bouncing back of α-particles was a big surprise to Rutherford. “It is
about as incredible as if you had fired an inch shell at a piece of tissue paper and it came
back and hit you”.-Rutherford

SELF-TEST QUESTIONS

i) Why do most of the α-particles pass through straight through the metal foil?
ii) Why some α-particles do appears to rebound from the metal foil?
iii) What factors will affect the extent of scattering of the α-particles?

Figure 1.3 Rutherford planetary or nuclear atomic model

7
From these observations, Rutherford concluded that
i) The mass of the atom and hence the positive charge was concentrated at the
centre of an atom in a tiny core which he called the nucleus.
ii) When the positively charged α-particles approached the positively charged
nucleus it was repelled and therefore sharply deflected.
iii) Electrons remained in the atom because they are strongly attracted to the
positively charged nucleus.

ACTIVITY
Describe the experimental basis for believing that the nucleus occupies a very small fraction
of the volume of the atom

For better understanding of the modern models, knowledge of wave mechanics is necessary.
The next section reviews some aspects of wave, especially electromagnetic wave.

1.2.3 The Nature of Electromagnetic Radiation

Much of our current understanding of the electronic structure of atoms has come from
analysis of the light emitted or absorbed by substances. To understand the basis for our
current model of electronic structure, therefore, we must first learn more about light. The
light that we can see with our eyes, visible light, is type of electromagnetic radiation.
Electromagnetic radiation carries energy through space in the form of wave.

Electromagnetic radiation consists of packets (quanta) of oscillating electric and magnetic

fields which are perpendicular to one another and traveling from the source in the form of a
harmonic wave.

8
There are many types of electromagnetic radiation in addition to visible light. These different
forms- such as the radio waves that carry music to our radios, the infrared radiation (heat)
from the glowing fireplace, and X-rays used in hospital, may seem very different from one
another, yet they share certain fundamentals characteristics.

ACTIVITY
List the types of the electromagnetic radiation, starting with the radiation having the longest
wavelength and ending with the radiation having the shortest wavelength

Figure 1.5 The Electromagnetic Spectrum

All types of electromagnetic radiation move through a vacuum at speed of 3.00x108 ms-1, the
‘speed of light’. Furthermore, they have wavelike characteristics.

9
 ACTIVITY

i) List the colours in the visible light

ii) Sketch a diagram of Newton’s experiment that demonstrated that white light is a
mixtures of colours

We will review some terminology used in wave.

To understand quantum theory, we must know something about the nature of waves. A wave
can be thought as a vibrating disturbance by which energy is transmitted. The speed of wave
depends on the type of wave and the nature of the medium through which the wave is
traveling (for example, air, water or a vacuum).

The harmonic wave is characterized by properties such as frequency,  wave length,  and
the wave number, -1.

Figure 1.4 Harmonic wave

The wave length  (Greek Lambda), is the distance between two successive crests or troughs
in a wave and is expressed in meters, m. The frequency  (Greek nu, pronounced as new) is

10
the number of waves passing a point in unit time (usually one second). Its unit is the Hertz;
Hz (i.e. cycles per second).

All electromagnetic radiation move through vacuum at a speed of 2.998x108ms-1 which is

called the speed of light c.

The wave length and frequency are related by:

c = 
where ν is the velocity of the wave in the medium. In vacuum
c = 2.998x108ms-1.

Common wavelength units for electromagnetic radiation

Unit Symbol Length /m Type of radiation
Angstrom Å 10-10 X-ray
Nanometer nm 10-9 Ultraviolet, visible
Micrometer µ 10-6 Infrared
Millimeter mm 10-3 Infrared
Centimeter cm 10-2 Microwave
Meter m 10 TV, radio

SELF-TEST QUESTIONS

i) What is the frequency of red light whose wavelength is 750 nm?

ii) What is the wavelength in nm whose frequency is 4.5x107Hz?

The reciprocal of frequency is the period of oscillation, T. It indicates the time taken for one
oscillation to pass a point. Hence,
1
T=

The reciprocal of the wavelength, -1, is known as the wave number. The wave number
indicates the number of waves accommodated in unit length. Thus, since

11
 c = 
then,
1 
= =
 c

The SI unit for wave number is reciprocal metres, m-1, although most of the literature values
are given in cm-1. The electric and the magnetic fields interact with matter leading to a
spectrum.

1.2.4 Plank’s Quantum Theory –Quantized Energy and Photons

Plank’s quantum theory state that, atoms and molecules emit or absorb energy
only in discrete quantities, like small packets or bundles.

The packets of electromagnetic radiation are known as quanta (singular: quantum) or

photons. Each photon has energy, E, given by:

E = h

where h = Planck’s constant = 6.6262x10-34J s photon-1.

υ= frequency of wave in Hertz

According to Plank’s quantum theory, energy is always emitted in whole number multiples of
h , for example 2h , 3h , 4h …., but never fractions

SELF-TEST QUESTIONS

1 For radiation having  = 2.0x10-7 m, calculate:

(i) E (kJmole-1)

12
 (ii) v
(iii) -1
2 Explain why X-ray is more energetic than microwave radiation
3 Briefly explain Plank’s quantum theory.
4 Give two familiar, everyday example to illustrate the concept of quantization

1.2.4 Hydrogen Spectrum

When sodium chloride is heated strongly in a Bunsen, it gives off a brilliant yellow light.
Some other also emits light when they are heated in this way. Have ever noticed that
compounds of one particular element always emit the same color of light when they behave
like this?

SELF-TEST QUESTIONS

1 What color of light is emitted by:

i) Potassium compounds
ii) Calcium compounds
iii) Copper compounds
2 What are emission spectra?
3 Distinguish line and continuum spectra

Some gaseous materials emit light when they are subjected to large potential differences in
electric discharge tubes. Neon advertising signs work in this way and the yellow sodium
street lamps are discharge tubes containing sodium vapour.

13
If the light emitted by these substances is examined using spectroscope, it is found not to
consist of a continuous range of colours like of spectrum of white light or colours in a
rainbow. Instead, the light emitted by these substances is composed of separate lines of
.different colour. This kind of spectrum is called a line. Each element display a
characteristic spectrum as first pointed out by Kirchhorff in 1859. The law governing the
distribution of lines in a spectrum was discovered by Balmer and Rydbeg. The interpretation
of this law in terms of atomic structure began with the work of Bohr in 1913. It revealed that
a study of spectra could provide a wealth of information about the atomic structure. The
study of these spectra has provided a key to the interpretation of many of the spectra of more
complex atoms.

In the visible region, the spectrum of hydrogen was known to consist of 4 main lines:
Red 656.3 nm
Blue 486.1 nm
Violet 434.0 and 410.2 nm
Denoted as Hα, Hβ, Hγ and Hδ.

Near the ultra violet there were other lines getting closer together converging to a limit of
364.6 nm

continous
H H H H spectrum
(ultravioltet)
434.0 nm
486.1 nm

364.6 nm
656.3 nm

(violtet)

410.2 nm
(red)
(red)

Figure 1.6 The Balmer series of atomic hydrogen excited by electric discharge. The dark
lines correspond to the bright emission lines of the spectrum.

14
 SELF-TEST QUESTIONS

Explain why lines getting closer together converging to a limit and continuum

It was discovered by Balmer as early as 1885, that the wavelength (λ) of the nine lines, then
known in this spectrum, could be accurately expressed by a single formula;

kn 2
= (1)
n2 − 22

Where k is a constant and n is an integer. The different wavelength corresponding to the

lines Hα, Hβ, Hγ and Hδ etc. are obtained by putting the integers 3, 4, 5, 6 etc respectively in
place of n. This set of line constitutes a spectral series and is known as the Balmer series.

Expressing in terms of wave numbers, equation (1) is rearranged as

1  1 1 
= = R 2 − 2  (2)
 2 n 
Where R is a constant called the Rydberg constant; R=109677.8 cm-1.
n was an integer which can take all values greater than 2, n=3,4, 5…∞.
 - the wave number, i.e. the number of wavelength in unit length.

The hydrogen spectrum was investigated in the far (UV) ultra violet, IR (infra red) regions
and revealed that there were few other series such as Lyman (UV region), Paschen and
Brackett and Pfund.

All these series were found to be in excellent agreement with the general equation

1  1 1 
= = R 2 − 2  (3)
  n1 n 2 
This is the universal formula for the atomic hydrogen spectrum.

15
Where n1 and n2 are integers somehow defining the energy stages of the atom.

The atomic spectrum of hydrogen atom

Series Region n1 n2
Lyman Ultraviolet 1 2, 3, 4, 5…..∞
Balmer Visible 2 3, 4, 5, 6…..∞
Paschen Near infrared 3 4, 5, 6, 7…..∞
Brackett Far infrared 4 5, 6, 7, 8…..∞
Pfund Far infrared 5 6, 7, 8, 9…..∞

Though equation (3) represented with great precision the entire known spectrum of atomic
hydrogen, it was however an empirical formula described from experiment. The
interpretation of this correct but un-derived formula was first given by theory of Niels Bohr
(1913).

1.2.5 Bohr Model of Atom (1913)

In order to explain the hydrogen spectrum, Bohr made the following assumptions governing
the behavior of electrons:
1. Electrons revolve in orbits of specific radius around the nucleus without emitting the
radiation.
2. Within each orbit, each electron has a fixed amount of energy; electrons in orbits
further from the nucleus have greater energies.
3. An electron may ‘jump’ from one orbit of high energy to another of lower causing the
energy difference to be emitted as a photon of electromagnetic radiation such as light.
4. An electron may absorb a photon of radiation and jump from a lower-energy orbit to a
higher-energy one.

The energy emitted or absorbed corresponds to the difference in the energy for the initial and
final state of the system.

16
 E final − Einitial = E = hv

Of the entire possible orbit only certain ones were acceptable – namely which had a specified
angular momentum. He assumed circular electron orbit with quantized electronic angular
momentum.

n=4 Increasing energy of the orbits

n=3

n=2

n=1

A photon is emitted with energy E=h

Figure 1.7. Bohr atomic model

One of the implication of these quantized energy states is that only certain photon energy are
allowed when electrons jump down from high to lower levels producing the hydrogen
spectrum.

17
n=6
n=5

n=4

n=3

n=2

n=1
Lyman Balmer Paschen Pfund
Brackett
series series series series
series

Figure 1.8. Various series in hydrogen spectrum.

For hydrogen the energy of electron in a n energy level is given by:

Z 2 me 4 1 −18 Z
2

En = − 2 2 2 = −2.18 x10 J
8h  0 n n2
or

Z 2 me 4 1 Z2
E n = − 2 2 2 = −13.6 2 eV
8h  0 n n
Where
m-mass of electron 9.1079x10-31 kg
e-electronic charge 1.602x10-19 C
h-Plank’s constant 6.626x10-34 J s
ε0-permitivity of free space 8.854188x10-12 C2 s2 kg-1 m-3
Z-nuclear charge

E = En2 − En1

18
 1 1
E = −2.18 x1018 Z 2  2 − 2  J
 n1 n2 
or
 1 1 
E = −13.6 Z 2  2 − 2  eV
 n1 n2 

SELF-TEST QUESTIONS

i) Calculate the frequency and wavelength of the emitted photon when electron drops
from the n=5 to the n=2 level in a hydrogen atom
Z 2 me 4 1
ii) Derive the expression E n = −
8h 2 02 n 2
iii) Explain why elements produce their own characteristic colors when they emit photons

1.2.5.1 Failures of the Bohr Model

While the model was a major step towards understanding the quantum theory of the atom, it
is not in fact a correct description of the nature of electron orbit.

Some of the shortcomings of the models are:-

1. It fails to provide any understanding why some spectral lines are brighter than others.
2. There is no mechanism for the calculation of transition probability.
3. The Bohr model treats electrons as if they were miniature planet with definite radius
and momentum. This is a direct violence of the Heisenberg uncertainty principle
which dictates that position and momentum cannot be simultaneously determined.

19
The Bohr model gives us a basic conceptual model of electrons orbit and energies. The
precise details of spectra and charge distribution must be left to quantum mechanical
calculations as with the Schrödinger equation.

ACTIVITY
1 What is an energy level? Explain the difference between a ground state and an
excited state
2 Explain the meaning of the negative sign in the Bohr’s equation
3 How does Bohr’s theory differ from concepts of classical physics?

20
 Lecture 2

2 Lecture 2 Objectives or Aims

At the end of this unit you should be able to;
(a) explain the dual nature of matter and wave
(b) describe qualitatively the Schrödinger equation and the
quantum numbers
(c) draw the shapes of atomic orbitals
(d) explain the Pauli’s exclusion principle and write electronic
configuration

2.0 Introduction

In this lecture, we will see that to explain phenomena at atomic and molecular level, classical
physics is inadequate, only the quantum theory will do. This Lecture describes the current
quantum model of an atom. Though, the concept requires knowledge of some mathematics
and physics, we will explain it, without rigorously solving those equations.

In high school you learnt electronic configuration of atoms.

• The electrons are arranged in energy levels, labeled n=1, 2, 3, 4 etc.
• That the maximum number of electrons in each energy level is given by 2(n) 2.
o The first energy level can have a maximum of 2(1)2=2
o The second energy level can have a maximum of 2(2)2=8
o The third energy level can have a maximum of 2(3)2=18
o And so on
No explanation was given at that time.

21
The table below gives the electronic configuration of the first twenty elements

Atom Atomic number Electronic configuration

H 1 1
He 2 2
Li 3 21
Be 4 22
B 5 23
C 6 24
N 7 25
O 8 26
F 9 27
He 10 28

ACTIVITY

Using the knowledge learnt in high school write the electronic configuration of the next ten
elements (i.e. sodium to calcium)
Atom Atomic number Electronic configuration
Na 11
Mg 12
Al 13
Si 14
P 15
S 16
Cl 17
Ar 18
K 19
Ca 20

22
We will now learn a more detailed method of writing electronic configuration of elements.

2.1.0 Quantum Model of an Atom

Our current understanding of the electronic structure of an atom is expressed in terms of

quantum mechanics. A fundamental concept of quantum mechanics is that all matter has
wave and particle-like properties.

2.2 De Broglie Equation- Dual Nature of Matter

Physicists were mystified but intrigued by Bohr’s theory. They questioned why is the
electron in Bohr atom restricted to orbiting the nuclear at fixed distances? In 1924 the French
physicist Louis de Broglie provided a solution to this puzzle. De Broglie reasoned as
follows: If light waves can behave like a stream of particles (photons), then perhaps particles
such as electrons possess wave properties.

•Light can behave both as a wave and as particles (photons). Likewise all matter (e.g.,
electrons, protons & neutrons) can also behave as waves.

From Einstein relativity theory, the fundamental law relating energy E, rest mass m0 and
momentum p of a particle is

2
E
  = p + m0 c
2 2 2

c

23
 E
The rest mass of a photon is zero, so m0=0 and therefore momentum is p =
c

From Plank’s quantum theory

E = h
Therefore E = h = mc
2

But p = mc

h h
p = mc = =
c 

h
Implying =
p

= wavelength of the moving particle;

h: Planck's constant 6.626 x 10-34 J.s

m: mass of the moving particle.

That is, all particles in motion have a wavelength that depends on the particle’s momentum.
The larger the momentum, the smaller the wavelength.

•In 1927, Davisson and Germer at Bell Laboratories showed that when a beam of electrons
was directed at a nickel crystal, a diffraction pattern was observed.

24
 2.2.1 Heisenberg Uncertainty Principle

Due to the dual nature of matter, both particles and wavelike properties, it is impossible to
simultaneously determine both the position and momentum of an object especially as small as
an electron. The position and momentum of a particle cannot be simultaneously measured
with high precision. There is a minimum for the product of the uncertainties of these two
measurements. There is likewise a minimum for the product of the uncertainties of the energy
and time.

h
xp 
2
Where Δx = uncertainty in position

Δp = uncertainty in momentum

This is not a statement about the inaccuracy of measurement instruments, nor a reflection on
the quality of experimental methods; it arises from the wave properties inherent in the
quantum mechanical description of nature. Even with perfect instruments and technique, the
uncertainty is inherent in the nature of things.

2.3 Wave-Like Property of an Electron

An electron in an atom is viewed as a standing wave. Some common examples of standing

waves are: a string attached at both ends to produce a musical tone in a guitar and violin.

25
 Figure 2.1 standing wave

We use the mathematical function Ψ (Greek Psi), called wavefunction to describe the wave-
like behavior of an electron in a region of space called the atomic orbital.
• Ψ has positive and negative amplitudes, like any wave.

Figure 2.2

• Due to the wave-like behavior of an electron, we cannot pin down its position and
momentum at the same time (Heisenberg Uncertainty Principle).
• In other words, we do not know the exact location of an electron and how it moves
from one spot to another in an atom.

26
 • Instead, we can only speak of the probability of finding an electron in a given
volume of space. This is given by the function Ψ2.

2.4 Schrödinger Wave Equation

• Based on the wave-particle dual nature of electron, Schrödinger developed a partial

differential equation to describe the behavior of an electron around an H atom. He received
Nobel Prize in 1933.

 2ψ  2ψ  2ψ 8π 2 m
+ + + (E − V )ψ = 0
x 2 y 2 z 2 h2
Schrödinger equation for a hydrogen atom

• This equation shows the relationship between the wave function of the electron Ψ, and
E and V, the total and potential energies of the system, respectively. The derivation of this
equation is beyond the scope of this course (will be derived in later).

• There are many solutions to the Schrödinger's equation. Each solution is represented
by the wave function, Ψ, which describes an atomic orbital. The Uncertainty Principle tells
us that we cannot pin down the exact location and momentum of an electron at the same time.
So chemists speak of "electron cloud" or electron density around a nucleus.

• An atomic orbital is defined as the boundary surface that encloses 95% of the electron
density for a particular wave function Ψ. Each atomic orbital (Ψ) may be uniquely defined
by a set of three quantum numbers:

n (the principal quantum number);

l (the orbital angular quantum number) and
ml (the magnetic quantum number).

27
• Since electron behaves as if it is spinning about an axis, a spin quantum number ms is
also required to uniquely describe an electron in an atomic orbital.

Figure 2.2 Spinning electron

28
 2.5 Quantum Numbers and their Properties

Symbol Name Allowed Properties

Values

N Principal n = 1, 2, 3, 4, • determines the size and energy of an atomic orbital

Quantum ...
• As n increases, the number of allowed orbitals
Number
increases, the size and energies of those orbitals also
increase.

L Orbital l = 0, 1, 2, ..., • Describe the shape of an atomic orbital

Quantum n-1
Number

ml Magnetic ml = -l, ..., -(l- • Describe the directionality of an atomic orbital

Quantum 1), 0, 1, 2, ...
Number +l

ms Spin ms = - ½, + ½ • Describes the orientation of the electron spin in space

Quantum
Number

Orbitals with different l values are known by the following labels:

L 0 1 2345…

Label s p dfgh…

29
Allowed values enable us to know the maximum number of electrons in each energy level

n l ml and ms
1 0 0
↑↓ 2 electrons in 1s orbital
Total of 2 electrons in the
first energy level
2 0 0
↑↓ 2 electrons in 2s orbital
1 -1 0 1
↑↓ ↑↓ ↑↓ 6 electrons in 2p orbital
Total of 8 electrons in the
first energy level; 2 in s
orbital and 6 in p orbitals
3 0 0
↑↓ 2 electrons in 3s orbital
1 -1 0 1
↑↓ ↑↓ ↑↓ 6 electrons in 3p orbital

2 -2 -1 0 1 2
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ 10 electrons in 3d orbital
Total of 18 electrons in the
first energy level; 2 in s
orbital, 6 in p orbitals and
10 in d orbitals

ACTIVITY
Using the same argument, show the maximum number of electrons for n=4.

30
 2.5.1 Relationship between quantum numbers and atomic orbitals

There is a relationship between the quantum numbers and the atomic orbitals. When l=0,
(2l+1)=1, and there is one value of ml; thus we have an s orbital. When l=1, (2l+1)=3, so
there are three values of ml; or three p orbitals, labeled px, py, and pz. When l=2, (2l+1)=5,
and there are five values of ml, and corresponding five d orbitals are labeled with more
elaborate subscripts. This is shown in the table 2.5.1 below.

n l ml Number of Atomic orbitals

orbitals Designation
1 0 0 1 1s

2 0 0 1 2s
1 -1 0 1 3 2px, 2py, 2pz

3 0 0 1 3s
1 -1, 0, 1 3 3px, 3py, 3pz
2 -2,-1, 0, 1,2 5 d xy , 3d yz , 3d xz , 3d x 2 − y 2 , 3d z 2

    
    

2.5.2 Electron Coordinates

The four quantum numbers n, l, ml and ms enable us to label completely an electron in any
orbital in any atom. For example, the four quantum numbers for a 2s orbital electron are n=2,
l=0, ml=o and either ms=+½ or ms=-½. In practice it is inconvenient to write out all the

31
individual quantum numbers, and so we use the simplified notation (n, l, ml, ms). For the
example above, the quantum numbers are (2, 0, 0, +½) or (2, 0, 0, -½). The value of ms has
no effect on the energy, size, shape, or orientation of an orbital, but it plays a profound role in
determining how electrons are arranged in an orbital.

2.5.3 The Pauli Exclusion Principle

This principle states that no two electrons in an atom can have the same four quantum
numbers. If two electrons in an atom should have the same n, l and ml values (that is, these
two electrons are in the same orbital), then they must have different values of ms. In other
words, only two electrons may exist in the same atomic orbital, and these electrons must
have opposite spins.

Consider the helium atom, which has two electrons. The three possible ways of placing two
electrons in the 1s orbital are as follows:

↑↑ ↓↓ ↑↓
1s2 1s2 1s2
(a) (b) (c)

Diagram (a) and (b) are ruled out by the Pauli Exclusion Principle. In (a), both electrons
have the same upward spin and would have the quantum numbers (1, 0, 0, +½); in (b), both
electrons have the downward spin and would have the quantum numbers (1, 0, 0, -½). Only
the configuration in (c) is physically acceptable, because one electron has quantum numbers
(1, 0, 0, +½) and the other has (1, 0, 0, -½). Thus the helium atom has the following
configuration:

He ↑↓
1s2

32
Note that 1s2 is read “one s two”, not “one s squared”.

SELF-TEST QUESTIONS

i) List the different ways to write the four quantum numbers that designate an electron
in a 3p orbital.
ii) List the different ways to write the four quantum numbers that designate an electron
in a 5d orbital

2.6 Atomic Wave functions

As we stated earlier, the concept quantum chemistry requires knowledge of some

mathematics and physics, we will explain it, without rigorously solving those equations. This
section introduces you to some of those concepts. It is meant to help you appreciate that
understanding of mathematics and physics theories are necessary to fully understand the
structure of atom. The pictorial diagrams in section 2.7 are mathematical functions derived
from those equations.

1. A wave function ψ describes an atomic orbital. For most calculations, it is simpler to

solve the wave equation if ψ is converted from the Cartesian coordinates (x, y, z) to spherical
Ψ coordinates (r, θ,φ). The two sets of coordinates are related by:

x = r sin  cos

y = r sin  sin 

z = r cos

33
Figure 2.6.1. The relationship between Cartesian and polar coordinates (diagram taken from
Atkins & Shriver).

2 In spherical coordinates, y can be factored into a radial wave function R, and an

angular wave function A:

( x , y , z ) = R( r ) A( , )

3 Radial wave function R(r):

• Describes how the electron density changes with distance from the nucleus
• s orbitals have finite electron density [ R(r )  0 ] at the nucleus but this drops off

exponentially as the distance from the nucleus increases.

• Other orbitals (e.g., p and d orbitals) have zero electron density [R (r) = 0] at the
nucleus.

34
Figure 2.6.2 Plot of Radial Wave function (in atomic units) versus distance r (in atomic
units) from the nucleus (diagram from Miessler & Tarr).

• The point at which the radial wave function R(r ) = 0 (except the origin) is called a

radial node.
• The sign of the radial wave function R (r) changes (from +ve to -ve or vice versa)
after passing the radial node
• The number of radial nodes for a given orbital is given by: [ n − (l − 1) ].

• ns orbitals have (n-1) radial nodes. E.g. 2s has 1 radial node.

• np orbitals have (n-2) radial nodes. e.g. 2p has 0 radial node, 3p has 1 radial node.
• nd orbitals have (n-3) radial nodes. E.g. 3d has 0 radial node, 5d has 2 radial nodes.
• nf orbitals have (n-4) radial nodes. E.g. 4f has 0 radial node.

• 1s orbital: no radial node.

• 2s orbital: two regions of maximum probability, separated by a spherical surface of
zero probability. (1 radial node)
• 3s orbital: Three regions of maximum probability, separated by two radial nodes.

35
Figure 2.6.3 Boundary surface diagram of s orbitals and electron density plots showing the
presence of radial nodes (diagram from Zumdahl).

Radial distribution function 4r R(r )

2
4

• Tells us where an electron will be most likely found at a given distance from the
nucleus.
• Plots of radial distribution functions for 1s, 2s and 3s orbitals show that there is at
least one maximum and the fact that an electron tends to be further from the nucleus as its
principal quantum number n increases. Therefore the size of an atomic orbital gets
increases as the principal quantum number n increases.
• Plots of radial distribution functions for 3s, 3p and 3d orbitals show that s orbital has
electron density closest to the nucleus than p and d orbitals. We say that an electron in a s
orbital is more penetrating than that in a p or d orbital.

36
Figure 2.6.4 Plot of radial distribution function 4r R(r ) for 1s, 2s,2p, 3s, 3p, 3d orbitals
2

of the hydrogen atom (diagram from Miessler & Tarr).

5 Angular wavefunction A( , )

• The angular wavefunction describes the shape of an atomic orbital and its orientation
in space.
• The angular function A( , ) is determined by the quantum numbers l and ml.

• Angular node (nodal plane): the plane(s) on which the angular

wavefunction A( , ) = 0 . The sign of the angular wavefunction changes (from +ve to -ve

or vice versa) after passing through an angular node.

37
 2.7 Pictorial Representation of Atomic Orbitals

• An atomic orbital is defined as a boundary surface which encloses 95 % of the

electron density for a particular Ψ.
• Atomic orbitals can be represented pictorially by boundary surface diagrams (H&S
Fig. 2.7.1, 2.7.2, 2.7.3) or electron density contour plots (see overhead).

s orbitals
• l = 0, ml = 0, the angular wave function A( , ) is independent of the angle q and f.

Therefore, an s orbital is spherically symmetrical about the nucleus.

Figure 2.7.1 Boundary surface diagram of an s orbital. (Figure taken from Shriver &
Atkins)

In two dimensions it is represented as:

38
 z

s orbital

p orbitals
• l = 1; ml = -1, 0, + 1. 3 possible orientation of p orbitals: along the x, y and z axes.
• Dumb-bell shaped; electron density concentrated in identical lobes on either side of
the nucleus.
• pz orbital has an angular node [ A( , ) = 0 ] along the xy plane; px orbital has an

angular node along the yz plane; py orbital has an angular node along the xz plane.
• The electron density contour map shows that there is no radial node for the 2p orbitals

but 1 radial node for the 3p orbitals. [see example 1]

Figure 2.7.2 Boundary surface diagram of p orbitals. The lightly shaded lobe has a positive
amplitude; the more darkly shaded lobe is negative (Figure taken from Shriver
& Atkins).

In two dimensions they are represented as:

39
 z
z
z

+
-
y - + y y
+
x - x x

pz py px

d orbitals

• l = 2, ml = -2, -1, 0, + 1, 2. There are five d orbitals.

• dxy, dyz, dxz, dx2-y2 have clover leaf shape and have 4 lobes of maximum electron
probability centered in the plane indicated in the orbital label. The four lobes are separated by
two nodal planes through the nucleus.
• dxy, and dx2-y2 are both centered in the xy plane while the lobes of dxy lie between
the axis.
• dz2 has two lobes along the z axis and a "belt" centered in the xy plane.

40
Figure 2.7.3 Boundary surface diagram of d orbitals. The lightly shaded lobe has a positive
amplitude; the more darkly shaded lobe is negative (Figure taken from Shriver &
Atkins).

In two dimensions they are represented as:

41
 y z
z

-
x - x y

dxz
dxy dyz

y
z

dx2-y2
dz2

The shaded lobe has a positive sign

Note the labelling of the axes

42
 2.8 Nodal Surfaces and Electron Density Contour Plots of Atomic
Orbitals

Figure 2.8. Electron density contour plots for selected atomic orbitals showing radial or
angular nodes (diagram taken from Miessler & Tarr).

2.9 Electronic Configuration

43
 2.9.1 Energy Levels in Hydrogen and Other Atoms

1 For H, the energy of the electron only depends on n, principal quantum number. The
s, p, d, f orbitals have the same energy.
2 In the ground state, the electron in the H atom resides on the 1s orbital.
3 For other atoms with more than one electron, electron-electron repulsion and
shielding play a role so energy depends on angular momentum quantum number l
as well as the principal quantum number n. The energies of the atomic orbitals in
multielectron atoms are arranged in the order:

ns < np < nd < n f

44
Figure 2.9.1. Orbital energy level diagrams for a hydrogen atom and multielectron atoms
(diagram taken from McMurry & Fay).
4 This ordering can be explained by considering the ability of having electron density
closest to the positively charged nucleus in different atomic orbitals.

Figure 2.9.2 Plot of radial distribution functions, 4 p r2R(r)2, for 1s, 2s, 2p, 3s, 3p, 3d
orbitals versus radius r (diagram taken from Cotton, Wilkinson & Gaus).

45
 The plot of radial distribution functions, 4 R(r ) , for 3s, 3p, 3d orbitals versus
2 2
5

radius (r) shows the first maximum for the s orbital is closest to the nucleus than the p or d
orbitals, i.e., the s orbital has electron density closest to the nucleus. We say that electrons in
an s orbital can penetrate closer to the nucleus than an electron in a p, d, or f orbital can.

• Since orbitals with electron density closer to the nucleus are more stable, therefore,
for a given n, the energy of the orbital increases in the order: s < p < d < f.
• The effect is so pronounced for d and f electrons that they lie at higher energy than the

46
s or p of the (n + 1 ) shell in some cases. E.g., Energy level of 3d > 4s, 4d > 5s; 4f > 5s, 5p.
Figure. Relative energy level of various atomic orbitals in a multielectron atom (diagram
from Rayner-Canham). Please note for the value of ns and (n - 1) d orbitals, there are
crossover points (e.g., 4s < 3d; 5s < 4d; 5s, 5p < 4f), this becomes important when filling
electrons in multi-electron atoms.

2.9.2 Electronic Configurations

•Describe how electrons distribute themselves in various orbitals in an atom.

We will learn the rules used in writing electron configurations for the elements. The process
is based on the Aufbau principle (The German word Aufbau means ‘building up’)

2.9.3 Aufbau Principle

• A set of rules guiding the filling order of orbitals.

1 Fill in electrons in the lowest energy orbital first.

2 Only two electrons with opposite spins per orbital (because Pauli Exclusion Principle
says that no two electrons in an atom can have the same four quantum numbers).
3 If two or more degenerate orbitals (i.e. orbitals with the same energy) are available,
electrons go into each degenerate orbital with parallel spins until the orbitals are half-
fill (Hund's rule).

47
 2.9.4 Order of Orbital Filling in Poly-electronic Atoms:

Figure 2.9.3 The order in which atomic orbitals are filled in a many electron atoms.
Start with the 1s orbital and move downward, following the direction of the arrows. Thus the
order goes as follows 1s→2s→2p→3s→3p→4s→3d→4p→5s→4d….

2.9.5 Filling of electrons for the first 30 elements

48
Filling of electrons for the first 30 elements

Atom Atom Electronic configuration

H H 1s1
He He 1s2
Li Li 1s22s1
Be Be 1s22s2
B B 1s22s22p1
C C 1s22s22p2
N N 1s22s22p3
O O 1s22s22p4
F F 1s22s22p5
Ne Ne 1s22s22p6
Na Na 1s22s22p63s1
Mg Mg 1s22s22p63s2
Al Al 1s22s22p63s23p1
Si Si 1s22s22p63s23p2
P P 1s22s22p63s23p3
S S 1s22s22p63s23p4
Cl Cl 1s22s22p63s23p5
Ar Ar 1s22s22p63s23p6
K K 1s22s22p63s23p64s1
Ca Ca 1s22s22p63s23p64s2
Sc Sc 1s22s22p63s23p64s23d1
Ti Ti 1s22s22p63s23p64s23d2
V V 1s22s22p63s23p64s23d3
Cr Cr 1s22s22p63s23p64s13d5
Mn Mn 1s22s22p63s23p64s23d5
Fe Fe 1s22s22p63s23p64s23d6
Co Co 1s22s22p63s23p64s23d7
Ni Ni 1s22s22p63s23p64s23d8
Cu Cu 1s22s22p63s23p64s13d10

49
Zn Zn 1s22s22p63s23p64s23d10

2.9.6 The Ground State Electron Configuration of the Elements*

Atomic Atom Electronic Atomic Atom Electronic Atomic Atom Electronic configuration
number configuration number configuration number
1 H 1s1 38 Sr [Kr]5s2 74 W [Xe]6s14f145d5
2 He 1s2 39 Y [Kr]5s24d1 75 Re [Xe]6s24f145d5
3 Li [He]2s1 40 Zr [Kr]5s24d2 76 Os [Xe]6s24f145d6
4 Be [He]2s2 41 Nb [Kr]5s24d3 77 Ir [Xe]6s24f145d7
5 B [He]2s22p1 42 Mo [Kr]5s14d5 78 Pt [Xe]6s14f145d9
6 C [He]2s22p2 43 Tc [Kr]5s24d5 79 Au [Xe]6s14f145d10
7 N [He]2s22p3 44 Ru [Kr]5s24d6 80 Hg [Xe]6s24f145d10
8 O [He]2s22p4 45 Rh [Kr]5s24d7 81 Tl [Xe]6s24f145d106p1
9 F [He]2s22p5 46 Pd [Kr]5s24d8 82 Pb [Xe]6s24f145d106p2
10 He 1s22s22p6 47 Ag [Kr]5s14d10 83 Bi [Xe]6s24f145d106p3
11 Na [Ne]3s1 48 Cd [Kr]5s24d10 84 Po [Xe]6s24f145d106p5
12 Mg [Ne]3s2 49 In [Kr]5s24d105p1 85 At [Xe]6s24f145d106p5
13 Al [Ne]3s23p1 50 Sn [Kr]5s24d105p2 86 Rn [Xe]6s24f145d106p6
14 Si [Ne]3s23p2 51 Sb [Kr]5s24d105p3 87 Fr [Rn]7s1
15 P [Ne]3s23p3 52 Te [Kr]5s24d105p4 88 Ra [Rn]7s2
16 S [Ne]3s23p4 53 I [Kr]5s24d105p5 89 Ac [Rn]7s26d1
17 Cl [Ne]3s23p5 54 Xe [Kr]5s24d105p6 90 Th [Rn]7s26d2
18 Ar [Ne]3s23p6 55 Cs [Xe]6s1 91 Pa [Rn]7s25f26d1
19 K [Ar]4s1 56 Ba [Xe]6s2 92 U [Rn]7s25f36d1
20 Ca [Ar]4s2 57 La [Xe]6s25d1 93 Np [Rn]7s25f46d1
21 Sc [Ar]4s23d1 58 Ce [Xe]6s24f15d1 94 Pu [Rn]7s25f6
22 Ti [Ar]4s23d2 59 Pr [Xe]6s24f3 95 Am [Rn]7s25f7
23 V [Ar]4s23d3 60 Nd [Xe]6s24f4 96 Cm [Rn]7s25f76d1

50
24 Cr [Ar]4s13d5 61 Pm [Xe]6s24f5 97 Bk [Rn]7s25f9
25 Mn [Ar]4s23d5 62 Sm [Xe]6s24f6 98 Cf [Rn]7s25f10
26 Fe [Ar]4s23d6 63 Eu [Xe]6s24f7 99 Es [Rn]7s25f11
27 Co [Ar]4s23d7 64 Gd [Xe]6s24f75d1 100 Fm [Rn]7s25f12
28 Ni [Ar]4s23d8 65 Tb [Xe]6s24f9 101 Md [Rn]7s25f13
29 Cu [Ar]4s13d10 66 Dy [Xe]6s24f10 102 No [Rn]7s25f14
30 Zn [Ar]4s23d10 67 Ho [Xe]6s24f11 103 Lr [Rn]7s25f146d1
31 Ga [Ar]4s23d104p1 68 Er [Xe]6s24f12 104 Unq [Rn]7s25f146d2
32 Ge [Ar]4s23d104p2 69 Tm [Xe]6s24f13 105 Unp [Rn]7s25f146d3
33 As [Ar]4s23d104p3 70 Yb [Xe]6s24f14 106 Unh [Rn]7s25f146d4
34 Se [Ar]4s23d104p4 71 Lu [Xe]6s24f145d1 107 Uns [Rn]7s25f146d5
35 Br [Ar]4s23d104p5 72 Hf [Xe]6s24f145d2 108 Uno [Rn]7s25f146d6
36 Kr [Ar]4s23d104p6 73 Ta [Xe]6s24f145d3 109 Une [Rn]7s25f146d7
37 Rb [Kr]5s1

*The symbol [He] is called the helium core and represents 1s2. [Ne] is called the neon core
and represents 1s2s2p6. [Ar] is called the argon core and represent [Ne]3s23p6. [Kr] is called
the krypton core and represents [Ar]4s23d104p6. [Xe] is called the xenon core and represents
[Kr]5s24d105p6. [Rn] is called the radon core and represents [Xe]6s24f145d106p6.

2 SUMMARY
1 Planks quantum theory state that energy is absorbed or emitted by atoms or molecules
in small discrete amounts (quanta), rather than over a continuous range. This is
governed by the equation E = hv
2 Light and matter have the characteristic of both particles(Dual nature of light and
matter)
3 The Schrödinger equation describes the motions and energies of subatomic particles
in terms of quantum theory. It tells us the possible energy states of the electron in an
atom or molecule and the probability of its location in a particular region surrounding
the nucleus.
4 An atomic orbital is a function that defines the distribution of electron density in
space. Orbitals are represented by electron density diagrams or boundary surface
diagrams.
5 Four quantum numbers are needed to characterize completely each electron in an
atom:

51
 • The principal quantum number n, which determines the main energy level, or shell of
the orbital;
• The angular momentum quantum number l, which determines the shape of the orbital;
• The magnetic quantum number, ml, which determines the orientation of the orbital in
space;
• And the electron spin quantum number ms, which relates only to the electrons spins on
its own axis.
6 Using the Aufbau (Building-up) principle we can determine the ground-state electron
configurations of all elements based on atomic number.

52
 Lecture 3

3 Lecture 3 Objectives or Aims

0020At the end of this unit you should be able to;
(a) arrange elements in the periodic table according to the group and period number
(b) discuss the periodicity of the periodic table

3.0 Introduction

We have just described the Aufbau principle of making probable assignments of electrons to
the atomic orbitals. There are over 103 known elements. Chemists have noted that many
elements show very strong similarities to one another. Recognition of periodic regularities in
physical and chemical behaviours and need to organize the large volume of available
information about the structure and properties of elemental substances led to the development
of the periodic table---a chart in which elements having similar chemical and physical
properties are arranged in groups. In this lecture you will learn how to place elements in
groups and periods

ACTIVITY
i) Read about historical development of the Periodic table: Mendeleev’s Periodic Table
and active rule
ii) Read about the American and European periodic tables

53
In high school you learnt the short form periodic table, where elements are arranged in
horizontals rows, called periods and vertical column called groups. The groups are numbered
from I to VIII (Roman numerals).

There are several controversies about the details of the periodic table that are still unresolved
despite the table’s existence for more than a century. For instance, there are three different
systems currently used to designate the vertical groups in the periodic table, namely, the
American, European and the modern International Union of Pure and Applied Chemistry
IUPAC format.
We will only discuss the modern periodic table in this lecture.

3.1.1 Modern Periodic Table - The Long Form

1 Elements are arranged with increasing atomic number in rows (called periods) and
columns (called groups).
2 Elements in Groups 1 and 2 are also called s block elements: valence electrons fill in s
orbitals.
3 Elements in Groups 13 to 18 are also called p block elements: valence electrons fill in
p orbitals.
4 Elements in Groups 1, 2 and 13 - 18 are called main group elements.
5 Elements in Groups 3 - 11 are called transition metal because they have partially filled
d orbitals. Elements in Groups 3 - 12 are called d block elements because valence
electrons filled in d orbitals.
6 f block elements (also called Lanthanides and Actinides): valence electrons filling in f
orbitals.
7 Elements in each group have similar valence-electron (electons in the outermost shell)
configuration and therefore similar properties.

54
 Figure 3.2. The structure of the periodic table (diagram from Atkins & Shriver).

3.1.2 Classifying the Elements into the Periodic Table

We will learn how to get the period and group numbers of the elements. This can be done in
three steps:
i) Write the electron configurations for the elements, using the Aufbau principle.
• The period number is the largest principal quantum number in the
electron configuration
• To get the group number, arrange the electrons in order increasing
principal quantum numbers, the group number is the sum of electrons
after the last p6 to be filled.
• * But for period 2 and 3, the group number is obtained as
“10+number of outer shell electrons”. Thus carbon and sulphur
are in group 14 and 16 respectively. This takes into account the
d-block elements in the short form periodic table.

55
 SELF-TEST QUESTIONS

i) Elements X and Y (not their actual symbols) have atomic number 13 and 82
respectively. To which period and groups do they belong?

Solution
The electronic configuration of:
X 1s22s22p63s23p1
Y 1s2s22p63s23p64s23d104p65s24d105p66s24f145d106p2
Period numbers
X the largest principal quantum number , n, is 3
Implying period 3
Y the largest principal quantum number , n, is 6
Implying period 6
Group numbers
X Electrons already arranged in ascending order according to the value of n.
Since it belong to period 3. Group number =10+3=13
Y Arranging electrons according to n
1s2s22p63s23p63d10 4s24p6 4d10 4f145s25p65d106s26p2
The last p6 to be filled is 5p6. The number of electrons after that
is=10+2+2=14
Implying group 14

ii) Nitrogen and Silver atomic number 7 and 47 respectively. To which period and
groups do they belong?

56
 Figure 3.1. The modern periodic table

3.2 Periodic Trends of Atomic Parameters

• Atomic properties such as effective nuclear charge, atomic radii, ionization energies,
electron affinity and electronegativity are important in accounting for the chemical
properties of an element.

57
 3.2.1 Shielding

1. In atoms with more than one electrons, the effect of electron-electron repulsion
depends on where the various electrons are located in the atom.

• Electrons in the outer shell (higher n) are pushed away by electrons in the inner shell
(lower n). As a result, the net nuclear charge (or effective nuclear charge, Zeff) felt by
an outer electron is substantially lower than the actual nuclear charge (Z). We say that
the outer electrons are shielded from the full charge of the nucleus by the inner
electrons.
• Electrons in the same shell (same n) have an immediate effect in shielding the nuclear
charge.
• Electrons in the outer shell (higher n) do not shield the nuclear charge from the inner
electrons (lower n)

• In 1930, Slater formulated a set of rules for the effective nuclear charge felt by
electrons in different atomic orbitals based on experimental data. The effective
nuclear charge Zeff can be calculated by the following equation:

• Zeff = Zactual - S
• Z: atomic number (number of protons);
• S: Slater screening constant or the number of shielding electrons (the number of non-
valence electrons)

3.3 Periodic Trend in Effective Nuclear Charge

Below is a table of the values of effective nuclear charge (Zeff) for s and p electrons in
elements Li - Ne:

58
Element Li Be B C N O F Ne

Z 3 4 5 6 7 8 9 10

1s 2.69 3.68 4.68 5.67 6.66 7.66 8.65 9.64

2s 1.28 1.91 2.58 3.22 3.85 4.49 5.13 5.76

2p 2.42 3.14 3.83 4.45 5.10 5.76

1. In the same atom, each electron with different n and l values can have a different Zeff
because the repulsive effects due to the other electrons is different. E.g., the Zeff for
the B atom: 1s >>2s > 2p and the size of orbitals is: 1s <<2s < 2p
2. For the same n and l value, Zeff increase across a period (e.g., from Li to Ne) as Z
increases. As a result, the size of the orbital decreases (electrons gets closer to the
nucleus) and the size of the atoms decreases. E.g. the Zeff for the 2p orbitals: B < C <
N < O < F < Ne and the size of the 2p orbitals is: B > C > N > O > F > Ne

3.4 Sizes of Atoms and Ions

• Since electrons can only be located by probability, there is no real boundary to an

atom.
• Radii of atoms and ions are obtained experimentally from measuring bond lengths in
molecules, metals and ionic crystals by X-ray diffraction.

1. Covalent radii rcov:

• Defined as the half-distance between the nuclei of two atoms of the same element
joined by a covalent bond.
• E.g., Cl2: bond distance = 198 pm, atomic radius of Cl = (198)/2 = 99 pm.

59
2. Van der waal radius rvdw:

• Defined as the half-distance between the nuclei of two non-bonded atoms or

molecules.
• Obtained from the closest approach between two non-bonded atoms or molecules in
the solid state.
• E.g., van der waal radius of Cl = 180 pm.
• In general, rvdw > rcov.

3. Ionic radius:

• Defined as the distance between the nuclei of adjacent cations and anions in a purely
ionic lattice.

In general, ranions > rcov > rcation for any given element.

• Cations: rNa+ = 116 pm; covalent radius rNa = 154 pm;

• Why? From Na (1s22s22p63s1) to Na+ (1s22s22p6): Zeff increases since no. of electrons
decreases.
• Anions: the covalent radius rCl = 97 pm; rCl- = 167 pm;
• Why? From Cl(1s22s22p63s23p5) to Cl- (1s22s22p63s23p6): Zeff decreases since no. of
electrons increases.

3.5 Periodic Trend in Atomic Radii

• Across a row, the atomic radius deceases because the n value for the outer shell
remains the same but Zeff is increasing.

60
 o E.g. For row stared by Na outer shell is 3s1, 3s2, 3s23p1, 3s23p2 ….,3s23p6,
atomic radius decreases (from Na to Ar) because the Z value is increasing and
the added electron do not completely shield the increase in Z.

• Down a group, the increase in Zeff does not completely counteract the fact that the
outer electrons are in orbitals with higher n, so radius increase down a group.
o E.g. For group headed by Be outer shell is 2s2, 3s2 , 4s2 , 5s2, 6s2, 7s2 , atomic
size increases from Be to Ra.

Table.3.5 Covalent radii (pm) of some selected elements

Li Be B C N O
132 89 82 77 77 73
Na Mg Al Si P S
154 136 118 111 106 102
K Ca Ga Ge As Se
203 174 126 122 120 117
Rb Sr In Sn Sb Te
216 191 144 140 140 136

Atomic Number

61
 3.6 Periodic Trend in Ionic Radii

Going down a group in cations and anions:

• e.g , Mg2+(2s22p6)--> Ca2+(3s23p6)--> Sr2+(4s24p6)--> Ba2+(2s22p6)
• e.g , F-(2s22p6)--> Cl-(3s23p6)--> Br-(4s24p6)--> I-(2s22p6)
• n value of outer orbital increase but not counteracted by the increasing Zeff.

Size of isoelectronic series (ions/atoms containing the same number of electrons):

• e.g , O2-(2s22p6)--> F-(2s22p6)--> Ne(2s22p6)--> Na+(2s22p6) --> Mg2+(2s22p6)
• Zeff increasing --> Since same no. of electrons and Z increasing.
• R)O2-)> r(F-)> r(Ne)> r(Na+)> r(Mg2+)

Ionic radii (pm) of some selected main group ions

Li+ Be2+ O2- F-

60 31 140 136
Na+ Mg2+ Al3+ S2- Cl-
95 65 50 184 181
K+ Ca2+ Ga3+ Se2- Br-
133 99 62 198
Rb+ Sr2+ In3+ Sn4+ Te2- I-
248 113 81 71 221 216

62
 3.7 Periodic Trend in the First Ionization Energy

The ionization potential of an atom is the minimum energy required to remove an electron
from a gaseous atom in its ground state. The magnitude of ionization potential is a measure of
the effort required to force an atom to give up an electron, the higher the ionization energy,
the more difficult it is to remove the electron.
For many-electron atom, the amount of energy required to remove the first electron from the
atom in its ground state is called the first ionization energy (I1)
The second ionization energy (I2) and the third ionization energy (I3) are shown in the
following equations
Energy + X+ (g) X2+ (g) + e-
Energy + X2+ (g) X3+ (g) + e-

Where X is the element and (g) denotes the gaseous state.

Higher ionization potentials labelled I2, I3, I4 and so on will correspond to the successive
removal of additional electrons. The table below gives the first ionization energies of the first
21 elements.

Table 3.7; Ionization Potential (Energy) for the First 20 Elements

Z Element First Second Third Fourth Fifth Sixth
1 H 1312
2 He 2373 5248
3 Li 520 7300 11808
4 Be 899 1757 14850 20992
5 B 801 2430 3660 25000 32800
6 C 1086 2350 4620 6220 38000 47232
7 N 1400 2860 4580 7500 9400 53000
8 O 1314 3390 5300 7470 11000 13000
9 F 1680 3370 6050 8400 11000 15200

63
 10 Ne 2080 3950 6120 9370 12200 15000
11 Na 495.9 4560 6900 9540 23400 16600
12 Mg 738.1 1450 7730 10500 13600 18000
13 Al 577.9 1820 2750 11600 14800 18400
14 Si 786.3 1580 3230 4360 16000 20000
15 P 1012 1904 2910 4960 6240 21000
16 S 999.5 2250 3360 3660 6990 8500
17 Cl 1251 2297 3820 5160 6540 9300
18 Ar 1521 2666 3900 5770 7240 8800
19 K 418.7 3052 4410 5900 8000 9600
20 Ca 589.5 1145 4900 6500 8100 11000

Ionization potentials are positive quantities.

If the ionization Energy was plotted against the atomic number, the periodicity will be clearly
evident. The 1st Ionization energy generally increases across the period.
Group I elements (alkali metals) have the lowest ionization energies. This is because the
elements have one valence electron that is effectively shielded by the completely filled inner
shells. Consequently, it is energetically easy to remove an electron from the atom of an alkali
metal to form unipositive ion (Li+, Na+, K+ …………….).

On the other hand non-metals have much higher ionization energies. The ionization energies
of the metalloids usually fall between those of metals and non-metals. This explains why
metals readily form cations while non-metals form anions.
However, there are irregularities in the increase of the ionization energy across the periods.
For example going across group 2 to 3, thus from Be to B and from Mg to Al. The group 3
elements have a single electron in the outermost sub level (ns2 np1), which is well shielded by
the inner electrons and the ns2 electrons.
Less energy is therefore needed to remove a paired s electron from the same principle energy
level. This brings about the lower ionization energies in group 3 elements compared with
those in group 2 in the same period.

• Periodic trends

64
 Atomic Number
Figure. Ionization energies of the first 55 elements

o Increase across each row, e.g. from Li to Ne; Na to Ar; K to Kr and so on (because
Zeff increases and the electrons in a given orbital are held more tightly, therefore, to
remove the electron from the atom requires more energy).
o Group 1 Alkaline metals (i.e. Li, Na, K, Rb, Cs and Fr) have minimum I.E. (due to
only single loosely held electron in the valence shell ns1).
o Group 18 Noble gases (i.e. He, Ne, Ar, Kr, Xe and Rn) have the highest I.E. (due to
filled valence shell, ns2np6; high Zeff valence electrons are tightly held).
o Minor irregularity occur from group 12 to group 13 elements also from group 15 to
group 16 elements:
o E.g. I.E. of Be (899.4 kJ/mol>I.E. of B (800.6 kJ/mol): due to completely
filled ns2 configuration (2s2 in Be vs 2s22p1 in B);
o I.E of N (1402.3 kJ/mol> I.E. of O (1313.9kJ/mol): due to half filled p orbital
in N (2s22p3 in N vs 2s22p4 in O);

o I.E decreases down a group, e.g. Li>Na>K>Rb>Cs>Fr; He>Ne>Ar>Kr>Xe>Rn.

o Due to electrons filling in larger shell (larger n), further away from the
nucleus. Therefore, valence electrons are well shielded from the nucleus by
inner shell electrons and are loosely held.

65
 o The ionization energy increase only slightly across a row in the transition or
lanthanides an actinides series.

SELF-TEST QUESTIONS

i) Explain why the first ionization energy of phosphorous is higher than that of
oxygen.
ii) Explain why the first ionization energy of magnesium is higher than that of
aluminum

iii) Why is the third ionization energy of Mg exceptionally higher than the second
ionization?

3.8 Periodic Trend in Electron Affinity

Electron Affinities
The electron affinity of an atom is defined as the energy change obtained when a neutral atom
in the gaseous state captures an electron. Thus, the energy is released by the reaction
represented below: -

X(g) + e-(g) →X- (g) + energy

It is the reverse of the 1st ionization potential and may be looked at as the ability of an atom to
accept one or more electrons. The largest electron affinities are those of the halogens. This is
as expected since the addition of one electron yields the stable octet configuration of the 18th
group elements-the noble gases.

66
X is an atom of an element. We assign a negative value to the affinity when energy is
released. The more negative the electron affinity, the greater the tendency of the atom to
accept an electron.
The tendency to accept electrons increases as we move from left to right across the periodic
table. Thus Electron Affinity becomes more negative. The E.A of metals are generally more
positive (or less negative) than those of non-metals. The values differ little within a group,
but the halogens have the most negative E.A values, while the noble gases that have filled
outer s and p sub shells have no tendency to accept electrons. The E.A of oxygen has a
negative value, which means that the process
O (g) + e- O- (g) is favourable
While that of the O- is
O- (g) + e- O2- (g) is positive (780kj/mol) meaning that this process is not
favourable in the gas phase.

3.9 Periodic Trend in Electronegativity

Electronegativity χ

67
The tendency of an atom to attract electrons to itself in a chemical bond is referred to as
electronegativity. The greater the electronegativity of an atom, the more strongly the atoms
attracts the electrons of a bond. This concept was proposed by Linus Pauling in 1937.
Electronegativity cannot be calculated accurately or measured directly. However, we expect
it to depend on the magnitude of the charge and on the distance of the bonding pair of
electrons from the nucleus. There are two important trends in electronegativity within the
periodic table: -
(a) electronegativity increases across a period as the charge increases
(b) electronegativity generally decreases from top to bottom in a group; because
with each successive shell, the bonding electrons are further from the nucleus.
Because the electronegativity of an atom cannot be defined quantitatively, it cannot be given
a precise value but approximate values. Table shows the electronegativity values

Table; Electronegativity χ of some elements

Group 1 2 13 14 15 16 17 18
Period
1 H He
2.2 -
2 Li Be B C N O F Ne
1.0 1.5 2.0 2.5 3.1 3.5 4.1 -
3 Na Mg Al Si P S Cl Ar
1.0 1.2 1.3 1.7 2.1 2.4 2.8 -
4 K Ca Ga Ge As Se Br Kr
0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1
5 Rb Sr In Sn Sb Te I Xe
0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4
Increase of electronegativity-----------------------------------------→

Important application: Could use χ to estimate bond polarity

68
 • Atoms with similar electronegativity (   0.4 ) form non-polar bonds.

• Atoms whose electronegativity differs by more than 2 form ionic bonds.

• Atoms whose electronegativity differs by less than 2 form covalent bonds.

3.10 Common Oxidation State of the Elements

Oxidation number is the apparent charge assigned to an atom in a molecule or in a

compound.
Some oxidation numbers are fixed:

Elements Oxidation number

O -2 except in peroxide
H +1 except in hydride
Group 1 metals +1
Group 2 metals +2
Halogens -1 except in oxygen compounds

3 SUMMARY
1 The experimental basis of the periodic table of the elements is periodic law: Certain
properties recur periodically when the elements are arranged by increasing atomic
number.
2 The theoretical basis is that the properties of an element are related to the electron
configuration of its atoms, and elements in the same group of the periodic table have
similar electron configuration.

69
 Lecture 4

Lecture 4 Objectives or Aims

At the end of this unit you should be able to;
(a) describe bonding in terms of Lewis structures
(b) use VSEPR to explain shapes of simple molecules
(c) use valence bond theory and hybridization to describe the
chemical bond

4.0 Introduction

We know a lot about chemical compound. We can determine their compositions and
formulas. We can represent reactions of compounds by chemical equations. We can do all
that without really having to consider the ultimate structure of atoms and molecules. We
know the shape of molecules that is arrangements of atoms in space define the chemistry of
molecules. In this lecture we will learn about the interaction between atoms called chemical
bonds. Most of our discussion will centre on Lewis theory, valence bond theory and
hybridization.

4.0 Electronic Structure and Chemical Bonding

There are four different but related approaches to explain how atoms combine to form
covalent bond:
1) Lewis dot structure.
2) Valence Shell Electron Pair Repulsion theory (VSEPR).
3) Valence bond theory (VBT) and hybridization of atomic orbital.
4) Molecular Orbital (MOT) Theory.

70
In this Lecture we will describe the interactions between atoms called chemical bonds. Most
of our discussion will centre on the simplest method of representing chemical bonding,
known as the Lewis theory. We will explore, however, other theories, one for prediction
probable shape-Valence – Shell Electron – Pair Repulsion (VSEPR) theory and Molecular
Orbital (MOT) theory for predicting Atomic Structure and Chemical Bonding, especially
covalent bonding.

4.1 Lewis Theory

Some fundamental ideas in Lewis theory are:

1. Electrons, especially those of the outermost (valence) electronic shell, play a
fundamental role in chemical bonding.
2. In some cases electrons are transferred from one atom to another. Positive and
negative ions are formed and attract each other through electrostatic forces called
ionic bonds.
3. In other cases one or more pairs of electrons are shared between atoms; this sharing
of electrons is called a covalent bond.
4. Electrons are transferred, or shared, in such a way that each atom acquires an
especially stable electron configuration. Usually this is a noble gas configuration, one
with eight outer shell electrons, or an octect.

4.1.1 Lewis Symbols and Lewis Structures

A Lewis symbol consists of a chemical symbol to represent the nucleus and core (inner shell)
electrons of an atom, together with dots placed around the symbol to represent the valence
(outer shell) electrons.

Examples.

71
Lewis structure for: Na electron configuration [Ne]3s1 is

Na

N electron configuration [He]2s22p3 is

O electron configuration [He]2s22p4 is

SELF-TEST QUESTIONS

1 Write the Lewis symbols for the following elements: H, He, Li, C, N, O, F, Ne, Cl,
Na, Mg, Al, K and Ca

A Lewis structure is a combination of Lewis symbols that represent either the transfer or
sharing of electrons in a chemical bond.

4.1.2 Ionic bonding (transfer of electrons)

+ -
Na + Cl Na Cl

-
Cl
2+
Mg + 2 Cl Mg -
Cl

4.1.3 Covalent bonding (sharing of electrons)

72
Hydrogen molecule is written showing a pair of dots between hydrogen atoms, indicating that
the hydrogen share the pair of electrons in covalent bond

H + H H H

Two hydrogen A hydrogen

atom molecule
The shared pair is usually represented by a line. E.g.

H H

Atoms other than hydrogen also form covalent bonds

H + Cl H Cl

Cl + Cl Cl Cl

A coordinate covalent bond, also known as a dative bond or coordinate bond is a kind of
2-center, 2-electron covalent bond in which the two electrons derive from the same atom. The
bonding of metal ions to ligands involves this kind of interaction.

SELF-TEST QUESTIONS

1 Write Lewis structures of the following ionic compounds:

73
 a) BaO; b) MgCl2; c) Aluminium oxide

2 Write Lewis structures of the following covalent compounds:

a) F2; b) H2O; c) NH3 d) CH4 e) O2 f) N2

4.1.4 Lewis Structures and Resonance

The Lewis structure of ozone O3 are:

Resonance structures are two forms of a molecule where the chemical connectivity is the
same but the electrons are distributed differently around the structure. Resonance occurs
when electrons can flow through neighboring pi systems.

Ozone does not have:

• One O=O double bond and
• One O-O single bond as individual structure imply, rather ozone has two equivalent
O-O bonds that one can think of as having a bond order of 1.5 midway between pure
single bond and pure double bond. Both have an identical length of 1.28 Å.

The idea of resonance between two or more Lewis structure is indicated by drawing the
individual Lewis structure and using double headed “resonance arrow” to show that both
contribute to the resonance hybrid.

74
 SELF-TEST QUESTIONS

Draw the resonance structure of carbonate ion, CO32-.

4.2 Molecular Geometry and Bonding Theories

(Molecular geometry or shape of molecules)

Lewis structures say nothing about bond angles.

4.2.1 Valence Shell Electron Pair Repulsion Theory (VSEPR)

❖ A structure should be considered which let all the electron pairs of the valence shell of
central atom try to get further away from each other. Repulsion between lone pairs is
greater than those between bonding electrons.

The order of repulsive energy is:

Lp-Lp>Lp-Bp>Bp-Bp

75
 O C O Linear

H Cl Linear

O
H H V-shaped

Cl

B Trigonal planar
Cl Cl

N
H H Triangular pyramidal
H

C H Tetrahedral
H H

4.2.3 Covalent Bonding and Orbital Overlap

The VSEPR model is a simple method which allows us to predict molecular geometry BUT it
does NOT explain why bond exist between atoms.

➢ How can we explain molecular geometry and basis of bonding at the same time?
o Quantum mechanism and molecular orbitals are used.

4.3 Valence Bond Theory (VBT)

76
 • Combine Lewis idea of electron pair bonds with electron orbitals (quantum
mechanics).
• Covalent bond occurs when atom shares electrons.
• Concentrate electron density between nuclei.
• The buildup of electrons density between two nuclei occurs when a valence atomic
orbital of one atom overlap with one of another.
• The orbital share a region of space i.e. they overlap.
• The overlap of orbital allows two electron of opposite spin to share the common space
between the nuclei forming a covalent bond.

• In the hydrogen m molecule for instance the H-H bond results from overlap of two
singly occupied H 1s orbitals.

H + H H H

1s 1s H2
molecule

• In the valence bond model, the strength of covalent bond depends on amount of
overlap. The greater the overlap, the stronger the bond. This in turn, means that bond
formed by overlap other than s- orbitals have directionalities to them.

In the fluorine molecule, F2, for instance each atom has electron configuration:

[He]2s22pz22py22px1

77
Meaning that the fluorine bond results from overlap of two singly occupied two 2p orbitals.
The 2p orbitals must point directly to one another for optimum overlap to occur, and the F-F
form bond along the orbitals.

F F
F + F

2p 2p F2
molecule
F F
atom atom

In HCl, the covalent bond involves overlap of 1s orbital (non-directional) with chlorine 3p
orbital and formed along p-axis.

1s 3p HCl molecule

The key ideas of valence bond theory can be summarized by few statements:
i. Covalent bonds are formed by overlap of atomic orbitals, each of which contains 1
electron of opposite spin.
ii. Each of the bonded atoms maintains its own atomic orbitals, but the electron pair in
the overlapping pair is shared by both atoms.
iii. The greater the amount of orbital overlap the stronger the bond. This leads to a
directional character to the bond when other than s – orbitals are formed.

4.4 Molecular Geometry and Hybrid Orbitals

78
Hybrid Orbitals
In chemistry, orbital hybridisation (or hybridization) is the concept of mixing atomic
orbitals into new hybrid orbitals (with different energies, shapes, etc., than the component
atomic orbitals) suitable for the pairing of electrons to form chemical bonds in valence bond
theory.
A hybrid orbital is an orbital formed by the combination of two or more atomic orbitals.
Hybrid orbitals are the result of a model which combines atomic orbitals on a single atom in
ways that lead to a new set of orbitals that have geometries appropriate to form bonds in the
directions predicted by the VSEPR model.
For polyatomic molecules we would like to be able to explain:
The number of bonds formed
Their geometries

sp Hybrid Orbitals

Consider the Lewis structure of gaseous molecules of BeF2:

• The VSEPR model predicts this structure will be linear

• What would valence bond theory predict about the structure?

The fluorine atom electron configuration:

• 1s22s22p5

• There is an unpaired electron in a 2p orbital

• This unpaired 2p electron can be paired with an unpaired electron in the Be atom to
form a covalent bond

79
The Be atom electron configuration:

• 1s22s2

• In the ground state, there are no unpaired electrons (the Be atom is incapable of
forming a covalent bond with a fluorine atom
• However, the Be atom could obtain an unpaired electron by promoting an electron
from the 2s orbital to the 2p orbital:

This would actually result in two unpaired electrons, one in a 2s orbital and another in a
2p orbital

• The Be atom can now form two covalent bonds with fluorine atoms
• We would not expect these bonds to be identical (one is with a 2s electron orbital, the
other is with a 2p electron orbital)

However, the structure of BeF2 is linear and the bond lengths are identical

• We can combine wavefunctions for the 2s and 2p electrons to produce a "hybrid"

orbital for both electrons
• This hybrid orbital is an "sp" hybrid orbital

80
 • The orbital diagram for this hybridization would be represented as:

Note:

• The Be 2sp orbitals are identical and oriented 180° from one another (i.e. bond
lengths will be identical and the molecule linear)
• The promotion of a Be 2s electron to a 2p orbital to allow sp hybrid orbital formation
requires energy.
o The elongated sp hybrid orbitals have one large lobe which can overlap (bond)
with another atom more effectively
o This produces a stronger bond (higher bond energy) which offsets the energy
required to promote the 2s electron

sp2 and sp3 Hybrid Orbitals

81
Whenever orbitals are mixed (hybridized):

• The number of hybrid orbitals produced is equal to the sum of the orbitals being
hybridized
• Each hybrid orbital is identical except that they are oriented in different directions

BF3

Boron electron configuration:

• The three sp2 hybrid orbitals have a trigonal planar arrangement to minimize electron
repulsion

NOTE: sp2 refers to a hybrid orbital being constructed from one s orbital and two p orbitals.
Although it looks like an electron configuration notation, the superscript '2' DOES NOT refer
to the number of electrons in an orbital.

• An s orbital can also mix with all 3 p orbitals in the same subshell

CH4

82
Thus, using valence bond theory, we would describe the bonds in methane as follows: each
of the carbon sp3 hybrid orbitals can overlap with the 1s orbitals of a hydrogen atom to form a
bonding pair of electrons

NOTE: sp3 refers to a hybrid orbital being constructed from one s orbital and three p
orbitals. Although it looks like an electron configuration notation, the superscript '3'
DOES NOT refer to the number of electrons in an orbital.

ANOTHER NOTE: the two steps often observed when constructing hybrid orbitals is to 1)
promote a valence electron from the ground state configuration to a higher energy orbital,
and then 2) hybridize the appropriate valence electron orbitals to achieve the desired
valence electron geometry (i.e. the correct number of hybrid orbitals for the appropriate
valence electron geometry)

H2O

Oxygen

83
 4.5 Hybridization Involving d Orbitals

Atoms in the third period and higher can utilize d orbitals to form hybrid orbitals

PF5

84
Similarly hybridizing one s, three p and two d orbitals yields six identical hybrid sp3d2
orbitals. These would be oriented in an octahedral geometry.

• Hybrid orbitals allows us to use valence bond theory to describe covalent bonds
(sharing of electrons in overlapping orbitals of two atoms)
• When we know the molecular geometry, we can use the concept of hybridization to
describe the electronic orbitals used by the central atom in bonding

Steps in predicting the hybrid orbitals used by an atom in bonding:

1. Draw the Lewis structure

2. Determine the electron pair geometry using the VSEPR model

3. Specify the hybrid orbitals needed to accommodate the electron pairs in the geometric
arrangement

NH3

1. Lewis structure

85
2. VSEPR indicates tetrahedral geometry with one non-bonding pair of electrons (structure
itself will be trigonal pyramidal)

3. Tetrahedral arrangement indicates four equivalent electron orbitals

H C
H
H

Valence Electron Pair Number of Orbitals Hybrid Orbitals

Geometry

Linear 2 Sp

Trigonal Planar 3 Sp2

Tetrahedral 4 Sp3

86
Trigonal Bipyramidal 5 sp3d

Octahedral 6 sp3d2

4.6 Multiple Bonds and Orbital Overlaps

Two types of bond

Sigma (σ) and pi (π) bonds

The "inter-nuclear axis" is the imaginary axis that passes through the two nuclei in a bond:

The covalent bonds we have been considering so far exhibit bonding orbitals which are
symmetrical about the inter-nuclear axis (either an s orbital - which is symmetric in all
directions, or a p orbital that is pointing along the bond towards the other atom, or a hybrid
orbital that is pointing along the axis towards the other atom)

Bonds in which the electron density is symmetrical about the inter-nuclear axis are termed
"sigma" or " σ " bonds

In multiple bonds, the bonding orbitals arise from a different type arrangement:

• Multiple bonds involve the overlap between two p orbitals

• These p orbitals are oriented perpendicular to the inter-nuclear (bond) axis

87
This type of overlap of two p orbitals is called a "pi" or "π" bond. Note that this is a single
π bond (which is made up of the overlap of two p orbitals)

In π bonds:

• The overlapping regions of the bonding orbitals lie above and below the inter-nuclear
axis (there is no probability of finding the electron in that region)
• The size of the overlap is smaller than a σ bond, and thus the bond strength is
typically less than that of a σ bond

Generally speaking:

• A single bond is composed of a σ bond.

• A double bond is composed of one σ bond and one π bond.
• A triple bond is composed of one σ bond and two π bonds.

C2H4 (ethylene; see structure above)

• The arrangement of bonds suggests that the geometry of the bonds around each
carbon is trigonal planar

88
 • Trigonal planar suggests sp2 hybrid orbitals are being used (these would be σ bonds)

What about the electron configuration?

Carbon: 1s2 2s2 2p2

• Thus, we have an extra unpaired electron in a p orbital available for bonding

• This extra p electron orbital is oriented perpendicular to the plane of the three sp2
orbitals (to minimize repulsion):

• The unpaired electrons in the p orbitals can overlap one another above and below the
internuclear axis to form a covalent bond

• This interaction above and below the inter-nuclear axis represents the single π bond
between the two p orbitals

89
Experimentally:

• we know that the 6 atoms of ethylene lie in the same plane.

• If there was a single σ bond between the two carbons, there would be nothing
stopping the atoms from rotating around the C-C bond.
• But, the atoms are held rigid in a planar orientation.
• This orientation allows the overlap of the two p orbitals, with formation of a π bond.
• In addition to this rigidity, the C-C bond length is shorter than that expected for a
single bond.
• Thus, extra electrons (from the π bond) must be situated between the two C-C nuclei.

C2H2 (acetylene)

• The linear bond arrangement suggests that the carbon atoms are utilizing sp hybrid
orbitals for bonding

• This leaves two unpaired electrons in p orbitals

• To minimize electron repulsion, these p orbitals are at right angles to each other, and
to the inter-nuclear axis:

• These p orbitals can overlap two form two π bonds in addition to the single σ bond
(forming a triple bond)

90
Delocalized Bonding

localized electrons are electrons which are associated completely with the atoms forming the
bond in question

In some molecules, particularly with resonance structures, we cannot associate bonding

electrons with specific atoms

C6H6 (Benzene)

Benzene has two resonance forms

• The six carbon - carbon bonds are of equal length, intermediate between a single bond
and double bond
• The molecule is planar
• The bond angle around each carbon is approximately 120°

The apparent hybridization orbital consistent with the geometry would be sp2 (trigonal planar
arrangement)

91
 • This would leave a single p orbital associated with each carbon (perpendicular to the
plane of the ring)

With six p electrons we could form three discrete π bonds

• However, this would result in three double bonds in the ring, and three single bonds
• This would cause the bond lengths to be different around the ring (which they are not)
• This would also result in one resonance structure being the only possible structure

The best model is one in which the π electrons are "smeared" around the ring, and not
localized to a particular atom

92
 • Because we cannot say that the electrons in the bonds are localized to a particular
atom they are described as being delocalized among the six carbon atoms

Benzene is typically drawn in two different ways:

• The circle indicates the delocalization of the p bonds

4.7 Resonance Structures and Hybrid Orbitals

Structure of NO3-

The Lewis structure of NO3- ion suggests that three resonance structures describe the
molecular structure

• For any individual Lewis resonance structure the electronic structure for the central N
atom is predicted to be sp2 hybrid orbitals participating in bonds with each of the O
atoms, and an electron in a p orbital participating in a bond with one oxygen
(forming a double bond)
• Two of the O atoms are predicted to have sp3 hybrid orbitals, with one orbital
participating in a σ bond with the central N atom and the other orbitals filled with

93
 non-bonding electron pairs. The other O atom is predicted to have sp2 hybrid orbitals,
with one orbital participating in a π bond with the central N and two orbitals filled
with non-bonding pairs of electrons. Furthermore, this last O atom is participating in a
double bond with the central N atom and therefore should have an electron in a p
orbital to participate in a π bond with the central N

How will this arrangement look as far as the orbital diagrams?

• There are 24 valence electrons in the expected valence orbitals above

• Summing the valence electrons from the formula gives: (3 x 6) for O, plus 5 for N,
plus 1 for ionic charge = 24

What might we expect for the electron configuration if we just started with the N atom?

94
 • We would predict that the N can only make two σ bonds, it would have one pair of
non-bonding electrons, and a p electron left over to participate in a π bond with one of
the π bonds
• This is different from what the Lewis structure shows, and from our prediction of
hybrid orbitals from the expected geometry
• If we look at the sp3 O atoms above we see that they actually have 7 electrons (1 more
than expected), while the sp2 O atom has the expected 6. Furthermore, the N atom (in
the correct sp2 configuration) has 4 electrons (1 less than expected)
• The "extra" electron from the ionic charge is correctly accounted for in the summation
of electrons

Thus, the correct way to determine electron configurations appears to be:

• begin by predicting the hybridization orbitals

• then determine lone pair arrangements and s and p bonding electrons for each atom
• confirm that all bonding electrons are correct and that the total of electrons is correct

4.8 Molecular Orbital Theory

Because arguments based on atomic orbitals focus on the bonds formed between valence
electrons on an atom, they are often said to involve a valence-bond theory.

95
The valence-bond model can't adequately explain the fact that some molecules contains two
equivalent bonds with a bond order between that of a single bond and a double bond. The
best it can do is suggest that these molecules are mixtures, or hybrids, of the two Lewis
structures that can be written for these molecules.

This problem, and many others, can be overcome by using a more sophisticated model of
bonding based on molecular orbitals. Molecular orbital theory is more powerful than valence-
bond theory because the orbitals reflect the geometry of the molecule to which they are
applied. But this power carries a significant cost in terms of the ease with which the model
can be visualized.

Forming Molecular Orbitals

Molecular orbitals are obtained by combining the atomic orbitals on the atoms in the
molecule. Consider the H2 molecule, for example. One of the molecular orbitals in this
molecule is constructed by adding the mathematical functions for the two 1s atomic orbitals
that come together to form this molecule. Another orbital is formed by subtracting one of
these functions from the other, as shown in the figure below.

One of these orbitals is called a bonding molecular orbital because electrons in this orbital
spend most of their time in the region directly between the two nuclei. It is called a sigma ()
molecular orbital because it looks like an s orbital when viewed along the H-H bond.
Electrons placed in the other orbital spend most of their time away from the region between
the two nuclei. This orbital is therefore called an antibonding or sigma star (*) molecular
orbital.

96
The bonding molecular orbital concentrates electrons in the region directly between the two
nuclei. Placing an electron in this orbital therefore stabilizes the H2 molecule. Since the *
antibonding molecular orbital forces the electron to spend most of its time away from the area
between the nuclei, placing an electron in this orbital makes the molecule less stable.

Electrons are added to molecular orbitals, one at a time, starting with the lowest energy
molecular orbital. The two electrons associated with a pair of hydrogen atoms are placed in
the lowest energy, or bonding, molecular orbital, as shown in the figure below. This diagram
suggests that the energy of an H2 molecule is lower than that of a pair of isolated atoms. As a
result, the H2 molecule is more stable than a pair of isolated atoms.

This molecular orbital model can be used to explain why He2 molecules don't exist.
Combining a pair of helium atoms with 1s2 electron configurations would produce a molecule
with a pair of electrons in both the bonding and the * antibonding molecular orbitals. The
total energy of an He2 molecule would be essentially the same as the energy of a pair of
isolated helium atoms, and there would be nothing to hold the helium atoms together to form
a molecule.

97
The fact that an He2 molecule is neither more nor less stable than a pair of isolated helium
atoms illustrates an important principle: The core orbitals on an atom make no contribution to
the stability of the molecules that contain this atom. The only orbitals that are important in
our discussion of molecular orbitals are those formed when valence-shell orbitals are
combined. The molecular orbital diagram for an O2 molecule would therefore ignore the 1s
electrons on both oxygen atoms and concentrate on the interactions between the 2s and 2p
valence orbitals.

Bond Order

The number of bonds between a pair of atoms is called the bond order. Bond orders can be
calculated from Lewis structures, which are the heart of the valence-bond model. Oxygen, for
example, has a bond order of two.

When there is more than one Lewis structure for a molecule, the bond order is an average of
these structures. The bond order in sulfur dioxide, for example, is 1.5 the average of an S-
O single bond in one Lewis structure and an S=O double bond in the other.

In molecular orbital theory, we calculate bond orders by assuming that two electrons in a
bonding molecular orbital contribute one net bond and that two electrons in an antibonding
molecular orbital cancel the effect of one bond. We can calculate the bond order in the O2
molecule by noting that there are eight valence electrons in bonding molecular orbitals and
four valence electrons in antibonding molecular orbitals in the electron configuration of this
molecule. Thus, the bond order is two.

98
Although the Lewis structure and molecular orbital models of oxygen yield the same bond
order, there is an important difference between these models. The electrons in the Lewis
structure are all paired, but there are two unpaired electrons in the molecular orbital
description of the molecule. As a result, we can test the predictions of these theories by
studying the effect of a magnetic field on oxygen.

Atoms or molecules in which the electrons are paired are diamagnetic; they are repelled by
both poles of a magnetic. Those that have one or more unpaired electrons are paramagnetic;
they are attracted to a magnetic field. Liquid oxygen is attracted to a magnetic field and can
actually bridge the gap between the poles of a horseshoe magnet. The molecular orbital
model of O2 is therefore superior to the valence-bond model, which cannot explain this
property of oxygen.

SELF-TEST QUESTIONS

i) What is molecular geometry? Why is the study of molecular geometry important?

ii) Describe the state of hybridization of arsenic in arsenic pentafluoride (AsF5).
iii) What is the difference between a Lewis dot symbol and a Lewis structure
iv) Define the following terms: lone pairs, the octet rule, sigma bond, pi bond and bond
length,

99
 Lecture 5

Lecture 5 Objectives or Aims

At the end of this unit you should be able to;
(a) State Arrhenius definition of an acid and bases
(b) describe Arrhenius, Brønsted and Lewis definitions of acids and bases
(c) calculate the pH of acids
(d) explain the buffers solutions

5.0 Introduction

The ideas about acids and bases (or alkalis) date back in ancient times. In secondary school
we learnt a number of things about acids and bases. In this lecture we will learn modern
acid-base theories, factors affecting the strength of acids and bases, the pH scale and the
calculation the pH.

5.0 Acid and Bases

Arrhenius definition of an acid is a substance that provides hydrogen ions, H+, when
dissolved in water, and one definition of a base is a substance that provides hydroxide ions,
OH- , when dissolved in water. Arrhenius definition of a base is restricted to those substances
which react with H+ ion to form water. In order to widen the scope of acid- base reaction and
include non-aqueous systems and a wider range of bases, Brønsted and Lowry independently
suggested the following definition in 1923.

100
 An acid is a proton donor

And

A base is a proton acceptor,

Thus the relationship between an acid and its corresponding base is

-
HB H+ + B
Acid proton base
proton donor proton acceptor

HB and B- are said to be conjugate and to form conjugate acid – base pair. HB is the
conjugate acid of B- and B- is the conjugate base of HB.

According to Brønsted – Lowry theory acid salts such as NaHSO4 and ammonium ion (NH4+)
are recognized as acid. What is more the definition of a base includes: all anions, water and
ammonia as well as oxides and hydroxides.

Acid Base Base Acid

HSO4- + OH- SO4- + H2O

NH4+ + OH- NH3 + H2O

2H3O+ + S2- H2O + H2S

+
H3O+ + NH3 H2O + NH4

H3O+ (hydroxonium ion)

NB/ On the equations above, water can act as a base and as an acid. It does this
simultaneously during its dissociation.

101
 +
H2O + H2O OH- + H3O

acid base base acid

5.1 Lewis Definition

Lewis acid - accept pair of electrons to form a covalent bond, for example BCl3 and AlCl3.

Whereas

Lewis base – donate pair of electrons to form a covalent bond, for example NH3, CH3NH2.

Soft acids - large cations with low charge density. e.g. Cs+ and Fr+.

Soft bases - large anions with low charge density. e.g. I-.

Hard acids - small cations with high charge density. e.g. Al3+.

Hard bases - small anions with high charge density. e.g. F-.

(Read about Fajan rules)

5.2 Ionic Equilibrium in Aqueous Solutions

102
Equilibrium involving ions in aqueous solution are important in industrial analytical and
biological processes. The principles and characteristics of these ionic equilibria are very
similar to those in other systems in chemical equilibria.

Two fundamental types of ionic equilibrium:

1. Equilibrium between undissolved solid solute and its dissolved product in solution are
solubility equilibrium.
2. The equilibrium between dissolved undissociated molecules and its dissolved ions,
i.e. dissociation equilibria.

In most cases this dissociation equilibria involve either acids or bases.

5.3 The Strength of the Acids and Bases

The strength of the acid is a measure of extent of dissociation.

The strength of different acids or bases can be compared using conductivity measurements.

Strong electrolytes such as HCl and NaOH are almost completely dissociated into ions in
aqueous solution. For example

HCl(aq) H
+
(aq) + Cl-(aq)

Almost completely dissociated or ionized

Strong acid

NaOH(aq) Na
+
(aq) + OH-(aq)

Almost completely dissociated or ionized

Strong base

103
Weak acids and bases are only partially ionized. For example

CH3COOH(aq) H
+
(aq) + CH3COO-(aq)

Ethanoic acid Only partially dissociated or ionized

weak acid

NH4OH(aq) NH4
+
(aq) + OH-(aq)

Only partially dissociated or ionized

Weak base

5.4 Quantitative Measurement of pH

In case of acids, relative strength can be compared by measuring the concentration of

hydrogen ions or by measuring their pH.

The “p” in pH comes from German word “potenz” meaning power and “H” from [H+]
concentration of hydrogen.

The pH of a solution is the negative logarithm to base 10 of the molar hydrogen ion
concentration i.e.

pH = − lg[ H + (aq) ]

Notice that the accepted abbreviation for logarithm to base 10 is lg not log.

Some useful mathematical expressions

lg xy = lg x + lg y

104
 lg x = lg x − lg y
y

lg x n = n lg x

For example lg10 2 = 0.3010 implying 10 0.3010 = 2

[H+] concentration in aqueous solution ranges from 10-15 to 10 mol dm-3, so it is convenient to
have a scale that is both negative and antilogarithmic. The negative sign produce positive pH
values for almost all solutions encountered in practice.

The logarithmic scale reduces the extremely wide variation in [H+(aq)] concentration to a
narrow range of pH from about 15 to -1.

Some worked examples

1. What is the pH of 10-1 mol dm-3 HCl (0.1 M HCl)?

Solution
Since HCl is fully dissociated and monobasic acid
[H+(aq)] in 10-1 mol dm-3 HCl=10-1 mol dm-3

pH = − lg[ H + ( aq) ] = − lg10 −1

= (−1) lg 10
=(-1)(-1)=+1

2. What is the pH of 10-3 mol dm-3 H2SO4 (0.001 M H2SO4)?

Since H2SO4 is fully dissociated and dibasic acid
[H+(aq)] in 10-3 mol dm-3 H2SO4=2x10-3 mol dm-3

pH = − lg[ H + ( aq) ] = − lg(2 x10 −3 )

= (−1) lg 2 x10 3
=(-1)(0.30-3)=+2.7

105
 3. The pH of pure water at 25 °C is 7. What is the hydrogen ion concentration?
Solution
pH = − lg[ H + (aq) ]

SELF-TEST QUESTIONS

What are the pH values of the following solutions?

a) 10-3 mol dm-3 HCl
b) 1.0 mol dm-3 HCl
c) 3 M HX which is only 50% dissociated

5.5 The Dissociation of Water

Water dissociate to form ions

H2O(aq) H
+
(aq) + OH-(aq)

The concentration of ions is very small as the pH of pure water shows. The equilibrium in
this reaction lies far to the left. Nevertheless we can write equilibrium constant.

[ H + ][OH − ]
Kc =
[ H 2 O]

1000
[H2O] in water = =55.56 mol dm-3 .This is a constant.
18

Thus we can incorporate the constant for [H2O] in the value of Kc.

106
 K c [ H 2 O] = [ H + ][OH − ] as a new constant Kw.

This overall constant Kw is called the ionic product for water.

At 25 °C [H+]=[OH-]=10-7

Hence Kw= [H+][OH-]=10-7x10-7

=10-14 mol2 dm-6

5.6 Important Generalization on Acids and Bases

• For neutral solutions [H+]=[OH-]=10-7 mol dm-3

And pH=7 at 25 °C

• For acidic solution [H+]>[OH-] and pH<7

• For basic alkaline solution [H+]<[OH-] and pH>7

1 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9

-11
10-12 10-13 10-14
10-10 10
[H+] mol dm-3

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Increasing acidity Increasing alkalinity

Neutral High pH
Lower pH Strong alkali
Strong acids

107
 5.7 Dissociation Constant of Acids and Bases

In dealing with acids, Kc is usually based on a symbol Ka which is known as dissociation

constant of the acid.

By eliminating aqueous state symbols, we can write

HB H+ + B-

[ H + ][ A − ]
Ka =
[ HA]

The numerical value of Ka provides an accurate measure of the extent to which an acid is
dissociated i.e. the strength of acid).

The stronger the acid, the greater the extent of dissociation, and hence the greater the Ka.

The value of Ka of some acids are given in the table below.

Acid Equilibrium equation Ka at 25 °C/ mol

dm3
H2SO4 + - Very large
H2SO4(aq) H (aq) + HSO4 (aq)

HNO3 + - 40
HNO3(aq) H (aq) + NO3 (aq)

HCOOH + - 1.6x10-4
HCOOH(aq) H (aq) + HCOO (aq)
- 6.4x10-5
C6H5COOH C6H5COOH(aq) H+(aq) + C6H5COO (aq)

CH3COOH + - 1.7x10-5
CH3COOH(aq) H (aq) + CH3COO (aq)

H2O + - 1.8x10-6
H2O(aq) H (aq) + OH (aq)

Worked example

108
The pH of 0.01 mol dm-3 of ethanoic acid (acetic acid), CH3COOH is 3.40 at 25 °C. What is
the dissociation constant of ethanoic acid at this temperature?

+ -
CH3COOH(aq) H (aq) + CH3COO (aq)

1 1-x 1-x
a a-x a-x

[ H + ][CH 3COO − ]
Ka =
[CH 3COOH ]

Since the concentration of hydrogen ions arising from water is much smaller than the
concentration of those from acid, we can say that;

[H+]=[CH3COO-]

And
[CH3COOH]=0.01-[H+]≈0.01
If H+]<<0.01, which it can be since ethanoic acid is a weak acid

pH = − lg[ H + ( aq) ] = 3.40

Hence lg[ H + ( aq) ] = −3.40 = −(4.00 + 0.6)

Therefore H+]=4x10-4 mol dm-3

And [CH3COO-]=4x10-4 mol dm-3

Now assuming [CH3COOH]=0.01 mol dm-3

[ H + ][CH 3COO − ] 4 x10 −4 x 4 x10 −4

Ka = =
[CH 3COOH ] 0.01

Ka=1.60x10-5 mol dm-3

109
By reversing this calculation, it is possible to predict the pH of solution of a weak acid. We
must, however, know the molarity of acid and its dissociation constant.

SELF-TEST QUESTIONS

1 What is the pH of 1.0 mol dm-3 of benzoic acid (C6H5COOH), given that
Ka(C6H5COOH)=6.4x10-5 mol dm-3.

5.8 Buffer Solutions

Are solutions that resist change in pH on addition of acid or alkali.

Or
A buffer solution change pH only slightly on the addition of small amount of either acid or a
base.

A buffer solution requires two components, one which is able to neutralize acids, and the
other able to neutralize bases. But, of course the two components must not neutralize each
other. Common buffer solutions are described either as a mixture of:

▪ a weak acid and its conjugate base or

▪ a weak base and its conjugate acid.

5.8.1 An Equation for Buffer Solutions

110
 The Hernderson-Hasslbebalch Equation
It is often useful to describe a buffer solution through an equation known as the Hernderson-
Hasslbebalch Equation. This equation is commonly used by biochemists and molecular
biologists. To derive this variation of the ionization constant expression, let’s consider a
mixture of a hupothetical weak acid, HA (such as CH3COOH), and its salt, NaA (such as
CH3COONa). We start with the familiar expressions

HA + H2O H3O
+
+ A-

[ H 3O + ][ A − ]
Ka =
[ HA]

And rearrange the right side of the Ka expression to obtain

[ A− ]
K a = [ H 3O + ]
[ HA]

Next, we take negative logarithm of each side of this equation.

[ A− ]
− lg K a = − lg[ H 3O + ] − lg
[ HA]

Now recalling that pH = − lg[ H 3O ] and pK a = − lg K a

+

[ A− ]
pK a = pH − lg
[ HA]
Then, we rearrange the equation to solve for pH

111
 [ A− ]
pH = pK a + lg
[ HA]

By recognizing the A- is the conjugate base of the weak acid HA, we can write somewhat
more general equation
[conjugateb ase]
pH = pK a + lg
[acid ]

Example. What is the pH a buffer solution made from 0.1 M acetic acid and 0.1 M
sodium acetate solution, given Ka (acetic acid=1.8x10-5 M)

Solution

[conjugateb ase]
pH = pK a + lg
[acid ]

0.10
pH = − lg(1.8 x10 5 ) K a + lg
0.10
4.74

An important example of a buffered system is that found in blood, which needs to be

maintained at a pH of 7.4.

5.8.2 Calculating pH Changes in Buffer Solutions

112
An important example of a buffered system is that found in blood, which needs to be
maintained at a pH of 7.4.

Addition of OH- to a buffer

Consider what happens when we add H3O+ or OH- to a buffer solution. First, suppose that we
add 0.01 mol of solid NaOH to 1.00 dm-3 of the 0.01 M acetic acid- 0.10 M sodium acetate
solution. Because a neutralization reaction involving strong acids or strong bases goes
essentially 100% to completion, we must take account of neutralization before calculating
[H3O+]. Initially, we have (1.00 dm-3)x(0.10 mol dm-3)=0.10 mol acetic acid and an equal
amount of acetate ion. When we add 0.01 mol of NaOH, the neutralization reaction will alter
the numbers of moles.

-
Neutralization reaction CH3COOH(aq) + OH (aq) H+(aq) + CH3COO-(aq)

Before reaction (mol) 0.10 0.01 0.10

Change (mol) -0.01 -0.01 +0.01
After reaction (mol) 0.09 ≈0 0.11

If we assume that the solution volume remains constant at 1.00 dm-3, the concentrations of
the buffer components after neutralization are

0.09mol
[CH 3CO2 H ] = = 0.09M
1.00dm −3

− 0.11mol
[CH 3CO2 ] = = 0.11M
1.00dm −3

Substituting these concentrations into the expression for [H3O+], we can then calculate the
pH:

[CH 3CO2 H ]
[ H 3O + ] = K a −
[CH 3CO2 ]

113
 0.09
= 1.8 x10 −5 = 1.5 x10 −5
0.11

pH=4.82

Adding 0.11 mol of NaOH changes [H3O+] by only a small amount because the concentration
ration [weak acid]/[conjugate base] changes by only a small amount, from unity to 9/11. The
corresponding change in pH, from 4.74 to 4.82, is only 0.08 pH unit

Addition of H3O+ to a buffer

Now suppose that we add 0.01 mol of HCl to 1.00 dm-3 of 0.10 M acetic acid – 0.10 M
sodium acetate buffer solution. The added strong acid will convert 0.01 mol of acetate ions
to 0.01 mol of acetic acid because of the neutralization

CH3COO-(aq) + H3O+(aq) H2O(aq) + CH3COOHaq)

The concentrations after neutralization will be [CH3COOH]=0.11 M and [CH3COO-]=0.09

M, and the pH of the solution will be 4.66

[CH 3CO2 H ]
[ H 3O + ] = K a −
[CH 3CO2 ]

0.11
= 1.8 x10 −5 = 2.2 x10 −5
0.09

pH=4.66
Again, the change in pH, from 4.74 to 4.66, is small because the concentration ratio[weak
acid]/[conjugate base] remains close to its original value

114
 SELF-TEST QUESTIONS

i) Explain what is meant by the strength of an acid.

ii) What are the Lewis definitions of an acid and a base? In what way are they more
general than the Brønsted definitions?

5 SUMMARY
1 Brønsted acids donate protons and Brønsted bases accept protons. Every Brønsted
acid has a conjugate Brønsted base and vice versa.
2 The acidity of an aqueous solution is expressed as its pH, which is defined as the
negative logarithm of the hydrogen ion concentration (in moles per litre). At 25 °C,
an acidic solution solution has pH<7, a basic solution has pH>7, and a neutral
solution has pH=7.
3 Lewis acids accept pairs of electrons and Lewis bases donate pairs of electrons to
form covalent bond.
4 A buffer solution is a combination of a weak acid and its weak conjugate; the
solution reacts with small amounts of added acid or base in such a way that the pH
of solution remains nearly constant. Buffer systems play a vital role in maintaining
the pH of body fluids.

115
 Lecture 6

Lecture 6 Objectives or Aims

At the end of this unit you should be able to;

(a) discuss the nuclear chemistry
(b) describe natural and artificial radioactivity
(c) balance nuclear equations
(d) describe and determine rate of radioactive decay and half-life
e) state uses of some radioactive isotopes

6.0 Introduction

So far we have studied chemical reactions. These originate from the electrons. We will now
discuss another phenomenon that originates within the nuclei of atoms. These phenomena
are referred to as nuclear chemistry.

6.0 Radioactivity

Radioactivity or radioactive decay- is the spontaneous decay of the nuclei of certain atoms,
accompanied by the emission of sub-atomic particles and / or high frequency electromagnetic
radiation.

116
 6.1 Characteristic of Radioactivity

All nuclei with atomic number greater than 83 are unstable and radioactive. They decompose
spontaneously with emission of radiation and energy. A radioactive change is not a chemical
reaction; it is a nuclear reaction that originates from the nuclei.

The decay product, if unstable will decompose further till a stable non-radioactive nuclear is
206 207
formed. All radioactive series found in nature give final stable isotopes 82 Pb , 82 Pb , and
208
82 Pb

6.2 Types of Radiation

Three types of radiations emitted by radioactive substance are: alpha particles (α-particles),
beta particles (β-particles) and gamma rays (γ-rays).

Alpha particles (α)

Alpha particles are positively charged Helium ions, He2+ i.e. Helium atom without electrons,
i.e. Helium nuclei containing two protons and two neutrons but no electrons.

They are normally represented as 24 He or just α.

Beta particles (β)

Beta particles are negatively charged fast moving electrons. They have much smaller mass
than alpha-particles. Since they are electrons, they are represented as −10 e . A beta particle is
not an electron outside a nucleus, but one formed when a neutron changes to a proton within
a nucleus.

117
 1n→1p + 0e
0 1 −1

Gamma rays (γ)

They are not material particles but high energy electromagnetic wave. They carry no charge.

SELF-TEST QUESTIONS

i) How do nuclear reactions differ from ordinary chemical reactions?

ii) Define nuclear fission, nuclear chain reaction and critical mass

iii) Explain how an atomic bomb work

iv) Explain how archeologists are able to tell the age of a fossil?

v) State the general rules for predicting nuclear stability

vi) How does Einstein’s equation, E = mc 2 , allow us to calculate nuclear binding energy?

6.3 Effect of Radioactive Decay on Parent Nuclide

Radioactive decay of α- and β-particles can change the number of protons and neutrons in the
nuclei of an atom.

6.3.1 α-Particle Decay

When an α-particle ( 24 He ) is emitted from nucleus both the atomic number and proton
number of the nucleus decrease. A new nuclide is formed.

118
Since the α-particle consists of two protons and two neutrons the atomic number is lowered
by 2 and mass number by 4 units.

Consider the nucleus of protactinium which emits α-particle to give a nuclide of actinium.
This is represented by the following equation.

233 Pa→ 229 Ac + 4He

91 89 2
Atomic number 91 89
Mass number 233 229

Results: Atomic number decrease by 2, mass number decrease by 4 when α-particle is

emitted.

In general
A X → A−4Y + 
Z Z −2

For example

238U → 234 Th + 4He

92 90 2

6.3.2 β-Particle Decay

When β-particle ( −10 e ) is emitted the atomic number increase by 1 and mass number remain
constant. This is because:

i. During the emission, a neutron in the nucleus spontaneously changes to a proton and
emit an electron (increasing the positive charge).
ii. The mass number remains constant because the mass of electron loss is negligible.

119
Consider the nuclide of radium, which emit β-particle to give a nuclide of actinium.

226 Ra→ 226 Th + 0e

−1
88 89

Results: Atomic number increase by 1, mass number remains constant when β -particle
is emitted

In general
A X → AY + 
Z Z +1

For example

234Th → 234 Pa + 0e
−1
90 91

6.3.3 γ-Particle Decay

The emission of gamma ray always accompanies other radioactive emissions. They are
produced when the remaining particles in the nuclei reorganizes. Generally, the gamma rays
are not shown when writing nuclei equation, because, they have no effect on mass number
and atomic number of the nuclide.

120
 6.4 Properties of Radiation

1 Penetrating Power
• Α-particles lowest; can be stopped a paper.
• Β-particles low; can be stopped a metal foil.
• γ -ray highest can only be stopped a thick lead metal.

2 Deflection in an electric field

• Α-particles deflected slightly toward the negative plate
• Β-particles deflected strongly toward the positive plate
• γ -rays not deflected

3 Effect of magnetic field

• Α-particles deflected slightly
• Β-particles deflected strongly
• γ -rays not deflected

4 Ionizing effect of radiation

• Α-particles Highly ionizing
• Β-particles weakly ionizing
• γ -rays do not ionize

6.5 Rate of Radioactive Decay

Radioactive decay is a random process. It is independent of temperature and pressure.

However, the probability to decay in any given interval time is the same for atoms present.

121
This means that the rate of radioactive decay is directly proportional to the number of atoms
present i.e. equal fraction of radioactive atom disintegrate in equal times. The decay rate
decreases with time.

This can be expressed mathematically:

Where M is the mass remaining at time t and

M0 is the mass at t=0
k is the Boltzmann constant
dM
 −M
dt

dM
= −kM
dt

M t
dM

M0 M
= −  kdt
t =0

M M
= e −kt or = exp(− kt )
M0 M0

M = M o e − kt or M = M o exp(−kt )

6.6 Half-Life, t½

The time required to reduce the original number of radioactive atom to half its value or the
time taken for half the mass of radioactive substance to decay.

122
The fraction of the original sample which remain after successful half-life:

t1/2 t1/2 t1/2 t1/2 t1/2

1 1 1 1 1
/2 /4 /8 /16 (etc)

Expressed mathematically

From M = M o e − kt or M = M o exp(−kt )

At half-life
M0
At t½ M=
2

M0
= M o e −kt
2

1
= e −kt
2

2 −1 = e − kt

ln 2 = kt 1
2

ln 2
= t1
k 2

123
Each radioactive material has its own half-life and value ranges from a small fraction of
second to thousands of years.

SELF-TEST QUESTIONS

1 Half-life of a radioactive element is 30 days. Calculate the time required for its
activity measured with G. M counter to drop from 4800 counts per minute to 300
counts per minute (ignore background counts).
2 State three uses of radioactive isotopes

6.7.1 Nucleus Fission

In nuclear fission a heavy nucleus (mass number> 200) divides to form smaller nuclei of
intermediate mass and one or more neutrons. For example:

235U + 1n→ 90Sr +143Xe +3 1n + Energy

92 0 38 54 0

6.7.2 Nucleus Fusion

In contrast to the nuclear fission, nuclear fusion, is the process of combining light nuclei into
heavier. For example:

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 2 H + 3H → 4He+ 1n + Energy
1 1 2 0

2 H + 1H → 4He + Energy
1 1 2

27 Al + 4He →30 P + 1n + Energy

13 2 15 0

6.7.3 Uses of Radio Isotopes

Radioactive isotopes have many applications in science and medicine. They are used in
carbon -14 dating, and determination of molecular structures. They are used to trace the path
of atoms of an element in a chemical reaction or biological processes, are called, tracers.
They are used in medical field. It must also be noted that high-energy damages living
systems by causing ionization and the formation of free radical.

6 Summary
1 Nuclear chemistry is the study of changes in the atomic nuclei. Such changes are
termed nuclear reactions.
2 Radioactive nuclei emit α-particles, β-particles and γ-rays.
3 Nuclear fission is the splitting of a large nucleus into two smaller nuclei plus
neutrons.
4 Nuclear fusion is the combination of two light nuclei to form one heavy nucleus.

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 Lecture 7
7.0 Redox Reactions

Lecture 7 Objectives or aims

At the end of this unit you should be able to;
(a) describe the redox reactions
(b) balance a redox reactions

7.0 Introduction

In high school, you learnt how to balance chemical equations. Some of those equations were
redox reactions that are relatively easy to balance. However, in laboratory we often
encounter more complex redox reactions, reactions that invariably involve oxoanoins such as
chromate (CrO42-), dichromate (Cr2O72-) , permanganate (MnO4-), nitrate(NO3-) and sulphate
(SO4-). In principle we can balance any redox equation using the basic procedures you learnt
in high school, but there are some special techniques for handling redox reactions, techniques
that also give us insight into electron transfer processes. In this lecture we will discuss two
system approach often used for balancing redox reaction: the oxidation number method and
the half-reaction method.

The next section define the redox reactions

7.1 Redox Reaction

Oxidation is defined as loss of one or more electron(s) by a substance, element, compound or

ion
Whereas

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Reduction is defined as gain of one or more electron(s) by a substance, element, compound or
ion.

Thus an oxidation – reduction reaction or REDOX reaction is a process in which electrons

are transferred from one substance to another.

Oxidation Reduction

A A+ + e-
B + e- B-

Reduction
Oxidation

7.2 How Can We Tell When Redox Reaction is taking Place?

We assign to atom a substance a value called oxidation number or oxidation state, which
provides a measure of an atom is neutral, electron rich or electron poor. By comparing
oxidation number of an atom before and after reaction, we can tell whether atom has gained
or lost one or more electron(s).

NB/ Oxidation number does not necessarily imply ionic charges. They are simply convenient
device to help us keep track of electrons in redox reaction. Whenever one substance lose one
or more electron(s) (oxidized) another substance must gain electron(s) (be reduced).

Reducing agent
Reducing agent loses one or more electron(s).
• undergo oxidation or
• Oxidation number of atom increase.

Oxidizing agent
Reducing agent gains one or more electron(s).
• undergo reduction or
• Oxidation number of atom decrease.

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 7.3 Balancing Redox Reaction

There are two system approach often used for balancing redox reaction:

I. The oxidation number method.

II. The half-reaction method.

7.3.1 Balancing Redox Reaction by Oxidation Number Method

The key to the oxidation-number method of balancing redox equation is to realize that the net
charge in the total of all oxidation number must be zero. That is any increase in oxidation
number for the oxidized atoms must be exactly matched by a corresponding decrease in
oxidation number of the reduced atoms.

Steps used in balancing a redox reaction by the oxidation number method

1. Write the unbalanced ionic equation.
2. Balance the equation for all atoms other than H and O.
3. Assign oxidation number to all atoms.
4. Decide which atom have changed oxidation number and by how much.
5. Find the total net increase in oxidation number for the oxidized atoms and the total net
decrease in oxidation number for the reduced atoms. Multiply the net increase and
the net decrease by a suitable number so that the two values become equal.
6. Balance the equation for oxygen by adding H2O to the side with less O and then
balance for hydrogen by adding H+ to the side with less H. Check your answer by
making sure that the equation is balanced both for atom and for charge.

Total increase in oxidation =Total decrease in oxidation Is equivalent as saying that

number (oxidation) number (Reduction) the total loss and gain of
electron(s) are equal in redox
reaction

Worked example
Balance the following redox reaction.
An aqueous acidic solution of the purple permanganate anion MnO4- is reduced by Br- to
yield the pale pink Mn2- ion along with Br2.

1 The unbalanced ionic equation for the process is:

MnO4-(aq) + Br-(aq) Mn2+(aq) + Br2(aq)

2 Balance the equation for all atoms other than H and O. Add a coefficient 2 for Br- to

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 add this coefficient to balance for Br_

MnO4-(aq) + 2Br-(aq) Mn2+(aq) + Br2(aq)

3 Assign oxidation numbers

MnO4-(aq) + Br-(aq) Mn2+(aq) + Br2(aq)

+7 +2 -1 +2 0

4 Decide which atom have changed oxidation number and by how much

MnO4-(aq) + Br-(aq) Mn2+(aq) + Br2(aq)

+7 -1 +2 0
Lose 2x1e-=2 e-

Gain 5 e-
5
Increase in oxidation numbers 2x(Br-1→Br0) net increase +2.

Decrease in oxidation numbers 2x(Mn+7→Mn+2) net decrease -5.

LCM of 2 and 5=10

(2x1)MnO4-(aq)+ 5x2Br-(aq) 2Mn2+(aq) + 5Br2(aq)

Multiply by these coefficient to make the net increase and net decrease
in oxidation number equal
6 Balance for O by adding H2O to the side with less O and then balance it by adding H+
to the side with less H.

-
2MnO4-(aq) + 10Br (aq) + 16H+(aq) 2Mn2+(aq) + 5Br2(aq) + 8H2O(l)

Add the H+ ions Add these water

to balance H mplecule to balance O
Charge: LHS: (2x-1)+(10x-1)+(16x+1)=+4 RHS: (2x+2)=+4

If everything has been done correctly, the final net ionic equation will result. The answer can
be checked by noting that the equation is balanced both for atom and for charge with +$ on
both sides.

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 7.3.2 Balancing Redox Reaction the Half-Equation Method

The key to this method is to realize that the overall reaction can be broken into two parts or
half-reaction. One half-reaction describes the oxidation part of the process and the other half-
reaction describes the reduction part. Each half is balanced separately and the two halves are
then added to obtain the final equation.

Steps used in balancing a redox reaction by half-reaction method

1. Write the unbalanced ionic equation
2. Decide which atoms are oxidized and which are reduced and write two unbalanced
half-reaction for the separate process.
3. Balance both half-reaction for all atoms other than H and O.
4. Balance both half-reaction for O by adding H2O to the side with less O and then
balance for H by adding H+ to the side with less H.
5. Balance both half-reactions for charge by adding electrons (e-) to the side with the
greatest positive charge. Then multiply the half-reactions by suitable number to make
the electrons count the same in both.
6. Add the two balanced half-reaction and cancel the electrons and any other species that
appears on both side of the equation. Check to see that both atoms and charge
balance and that the coefficients are reduced to simplest whole number.

Worked example
Let’s look at the reaction of aqueous potassium dichromate (K2Cr2O7) with aqueous sodium
chloride to see how this method works. The reaction occurs in acidic solution according to
the unbalanced equation:
1
Cr2O72-(aq)+ Cl-(aq) Cr3+(aq) + Cl2(aq)

2 The first step is to decide which atoms have been oxidized and which have been
reduced. In the present case, the chloride atom is oxidized (from -1 to 0), and the chromium
atom is reduced (from +6 to +3). Thus, we can write two unbalanced half-reactions that show
the separate steps:

Oxidation half-reaction
Cl-(aq) Cl2(aq)

Reduction half-reaction
Cr2O72-(aq) Cr3+(aq)

3 With the two half-reactions identified, each is balanced separately. Begin by

balancing for all atoms other than H and O. The oxidation half- reaction needs a coefficient
of 2 before the Cl-, and the reduction half-reaction needs a coefficient of 2 before the Cr3+.

Oxidation

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 Add this coefficient
to balace for Cl

2Cl-(aq) Cl2(aq)

Reduction
Add this coefficient
to balance for Cr

Cr2O72-(aq) 2Cr3+(aq)

4 Next, balance both half-reactions for oxygen by adding H2O to the side with less O,
and balance for hydrogen by adding H+ to the side with less H. The oxidation half-reaction
has no H or O, but the reduction reaction needs 7H2O on the product side to balance for O
and 14H+ on the reactant side to balance for H:

Oxidation
2Cl-(aq) Cl2(aq)

Reduction
Then, add 14 H+ to
First, add 7H2O to
balance for H
balance for O

Cr2O72-(aq) + 14H+(aq) 2Cr3+(aq) + 7H2O(l)

5 Now, balance both half-reactions for charge by adding electrons (e-) to the side with
the greater positive charge. The oxidation half-reaction must have 2 e-added to the product
side, and the reduction half-reaction must have 6 e- added to the reactant side:

Oxidation
Add these elecctrons
to balance charge

-
2Cl-(aq) Cl2(aq) + 2e

Reduction
Add these electrons to
balance for charge

Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O(l)

With both half =-reactions now balanced, we need to multiply by suitable coefficient so that
the number of electrons released in the oxidation half-reaction is the same as the number

131
consumed in the reduction half-reaction. Since the reduction half-reaction has 6 e- but
oxidation half-reaction has only 2 e-, the entire oxidation half-reaction must be multiplied by
3.

Oxidation
Multiply by this coefficient to equilize the
number of electrons in the two half-reactions

-
3x[2Cl-(aq) Cl2(aq) + 2e ]

or 6Cl-(aq) 3Cl2(aq) + 6e- ]

Reduction
Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O(l)

6 Adding the two half-reactions together, and canceling the species that occur on both
sides (only electrons in this example), then gives the final balanced equation. Check the
answer to make sure it is balanced both for atoms and for charges

6Cl-(aq) 3Cl2(aq) + 6e-

Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O(l)

Cr2O72-(aq) + 14H+(aq) + 6Cl- 2Cr3+(aq) + 7H2O(l) + 3Cl2(aq)

Charge: (-2)+(+14)+(6x-1)=+6 Charge: (2x+3)=+6

Study questions

1 Assign the oxidation numbers of the underlined elements

a) ClO3- b) SO32- c) Mn2O7 d) OsO4

2 Balance the following equations:

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 Fe2+(aq) + MnO4-(aq) Fe3+(aq) + Mn2+(aq) (in acidic solution)

Fe2+(aq) + H2O2(aq) Fe3+(aq) + H2O(l) (in acidic solution)

H2O2(aq) + Mn2-(aq) MnO2(s) + H2O(l) (in basic solution)

Fe2+(aq) + Cr2O72-(aq) Fe3+(aq) + Cr3+(aq) (in acidic solution)

7 Summary
1 There are two related definitions of redox, involving electron transfer, the other
involving the concept of oxidation number.

2 In terms of electron transfer, oxidation is defined as a loss of electrons, and reduction

is defined as a gain of electrons.

3 Electron-transfer reactions are called redox reactions.

4 An oxidation number is a number assigned to an atom or ion to describe its relative

state of oxidation or reduction state. Using oxidation numbers it is possible to decide
whether redox has occurred.

5 In terms of oxidation numbers, oxidation is defined as an increase in oxidation

number and reduction is defined as a decrease in oxidation number.

6 There are two system approach often used for balancing redox reaction, the oxidation
number method and the half-reaction method.

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 Lecture 8
Intermolecular forces
Van der Waals’ forces
Hydrogen bonding
Structures and shapes of simple molecules
Stoichiometry
The mole concept
Volumetric analysis
Balancing of equations

134
 8.1: Intramolecular and intermolecular forces
There are two kinds of forces, or attractions, which operate in a molecule — intramolecular
and intermolecular.
Intramolecular forces are the forces that hold atoms together within a molecule.
Intermolecular forces are forces that exist between molecules.

Types of intramolecular forces of attraction

1. Ionic bond: This bond is formed by the complete transfer of valence electron(s)
between atoms. It is a type of chemical bond that generates two oppositely charged
ions. In ionic bonds, the metal loses electrons to become a positively charged cation,
whereas the nonmetal accepts those electrons to become a negatively charged anion.

2. Covalent bond: This bond is formed between atoms that have similar
electronegativities—the affinity or desire for electrons. Because both atoms have
similar affinity for electrons and neither has a tendency to donate them, they share
electrons in order to achieve octet configuration and become more stable.
A nonpolar covalent bond is formed between same atoms or atoms with very similar
electronegativities—the difference in electronegativity between bonded atoms is less than
0.5.

135
A polar covalent bond is formed when atoms of slightly different electronegativities share
electrons. The difference in electronegativity between bonded atoms is between 0.5 and 1.9.
Hydrogen chloride HF, Water H2O and Hydrogen Fluoride HF are all examples of polar
covalent bonds.

3. Metallic bonding: This type of covalent bonding specifically occurs between atoms
of metals, in which the valence electrons are free to move through the lattice. This
bond is formed via the attraction of the mobile electrons—referred to as sea of
electrons—and the fixed positively charged metal ions. Metallic bonds are present in
samples of pure elemental metals, such as gold or aluminum, or alloys, like brass or
bronze.

The freely moving electrons in metals are responsible for their a reflecting property—
freely moving electrons oscillate and give off photons of light—and their ability to
effectively conduct heat and electricity.

136
Intermolecular forces of attraction
Now let’s talk about the intermolecular forces that exist between molecules.
Intermolecular forces are much weaker than the intramolecular forces of attraction but are
important because they determine the physical properties of molecules like their boiling
point, melting point, density, and enthalpies of fusion and vaporization.
Types of intermolecular forces that exist between molecules
1. Dipole-dipole interactions: These forces occur when the partially positively charged
part of a molecule interacts with the partially negatively charged part of the
neighboring molecule. The prerequisite for this type of attraction to exist is partially
charged ions—for example, the case of polar covalent bonds such as hydrogen
chloride, Dipole-dipole interactions are the strongest intermolecular force of
attraction.

2. Hydrogen bonding: This is a special kind of dipole-dipole interaction that occurs

specifically between a hydrogen atom bonded to either an oxygen, nitrogen, or
fluorine atom. The partially positive end of hydrogen is attracted to the partially
negative end of the oxygen, nitrogen, or fluorine of another molecule. Hydrogen
bonding is a relatively strong force of attraction between molecules, and considerable
energy is required to break hydrogen bonds. This explains the exceptionally high
boiling points and melting points of compounds like water and hydrogen fluoride.

137
 Hydrogen bonding plays an important role in biology; for example, hydrogen bonds
are responsible for holding nucleotide bases together in DNA and
RNA.

3. London dispersion forces, under the category of van der Waal forces: These are
the weakest of the intermolecular forces and exist between all types of molecules,
whether ionic or covalent—polar or nonpolar. The more electrons a molecule has, the
stronger the London dispersion forces are. For example, bromine, has more electrons
than chlorine, so bromine will have stronger London dispersion forces than chlorine,
resulting in a higher boiling point for bromine, compared to chlorine. Also, the
breaking of London dispersion forces doesn’t require that much energy, which
explains why nonpolar covalent compounds like methane, oxygen, and nitrogen—
which only have London dispersion forces of attraction between the molecules—
freeze at very low temperatures.

4. Ion-Dipole Interaction
Ion-dipole interaction occurs when an ion encounters a polar molecule. In this case,
the charge of the ion determines which part of the molecule attracts and which repels.
A cation or positive ion would be attracted to the negative part of a molecule and
repelled by the positive part. An anion or negative ion would be attracted to the
positive part of a molecule and repelled by the negative part.
Example: An example of the ion-dipole interaction is the interaction between a Na+
ion and water (H2O) where the sodium ion and oxygen atom are attracted to each
other, while the sodium and hydrogen are repelled by each other.

138
 How forces of attraction affect properties of compounds
Polar covalent compounds—like hydrogen chloride, have dipole-dipole interactions
between partially charged ions and London dispersion forces between molecules.
Nonpolar covalent compounds—like methane and nitrogen gas, only have London
dispersion forces between molecules. The rule of thumb is that the stronger the
intermolecular forces of attraction, the more energy is required to break those forces. This
translates into ionic and polar covalent compounds having higher boiling and melting
points, higher enthalpy of fusion, and higher enthalpy of vaporization than covalent
compounds.
8.2: Structures and shapes of simple molecules

Molecular geometry, also known as the molecular structure, is the three-dimensional

structure or arrangement of atoms in a molecule. Understanding the molecular structure of a
compound can help determine the polarity, reactivity, phase of matter, color, magnetism, as
well as the biological activity.

To determine the shapes of molecules, students must become acquainted with the Lewis
electron dot structure. Although the Lewis theory does not determine the shapes of
molecules, it is the first step in predicting shapes of molecules. The Lewis structure helps us
identify the bond pairs and the lone pairs. Then, with the Lewis structure, students apply the
valence-shell electron-pair repulsion (VSPER) theory to determine the molecular
geometry and the electron-group geometry.

To identify and have a complete description of the three-dimensional shape of a molecule,

students need to know also learn about state the bond angle as well. Lewis Electron Dot
Structures play crucial role in determining the geometry of molecules because it helps us
identify the valence electrons.

139
 8.3: Stoichiometry
Stoichiometry is a section of chemistry that involves using relationships between reactants
and/or products in a chemical reaction to determine desired quantitative data.
The mole concept

A concept used for measure amount of particles like atoms, molecules.

Atomic Mass Unit with Examples

Since atoms are too small particles we cannot measure their weights with normal methods.
Thus, scientist found another way to measure mass of atoms, molecules and compounds.
They approve one atom of carbon isotopes 6C12 as 12 atomic mass unit. Mass of every
elements expressed in terms of atomic mass unit is called relative atomic mass. We can also
calculate relative molecule mass with same method; adding individual atomic masses of
elements gives us relative molecular mass. For example;

1 H atom is 1 amu (amu=atomic mass unit)

1 Ca atom is 40 amu

1 Mg atom is 24 amu

1 H2O molecule includes 2 hydrogen atoms and one oxygen atom;

(2.1)+(16)=18 amu

The Mole Concept and Avogadro's Number

A concept used for measure amount of particles like atoms, molecules. Number of atoms in
the 6C12 element is equal to 1 mole. Number of particles in 1 mole is called Avogadro's
number; 6.02.x1023.

1 mole atom contains 6.02x1023 atoms

1 mole molecule contains 6.02x1023 molecules

1 mole ion contains 6.02x1023 ions

Mole=Number of Particles/Avogadro's Number

Example: Find the mole of molecule including 1.204x1023 NH3?

Solution:

1 mole NH3 contains 6.02x1023 molecule

X mole NH3 contains 1.204x1023 molecule

___________________________________________

140
x= 0.2 mole NH3 molecule

We can solve this problem using formula given above;

Mole=Number of Particles/Avogadro's Number

Mole=1.204x1023/ 6.02x1023 = 0.2 mole

The Mole Concept Exams and Problem Solutions

1. If atomic mass of Mg atom is 24 g, find mass of 1 Mg atom.

Solution:

We can solve this problem in two ways;

1st way:

6.02x1023 amu is 1 g

24 amu is ? g

¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯

?=4x10-23 g

2nd way;

1 mol Mg (6.02x1023 Mg atoms) is 24 g

6.02x1023 Mg atoms 24 g

1 Mg atom ?g

¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯

?=4x10-23 g

2. Find mass of 1 molecule C2H6. (C=12, H=1)

Solution:

C2H6=2.12+6.1=30

6.02x1023 C2H6 molecule is 30 g

1 C2H6 molecule is ? g

¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯

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1 C2H6 molecule is =?=5.10-23 g

3. Find mole of 6.9 g Na. (Na=23)

Solution:

23 is the atomic mass of Na, in other words 1 mole Na is 23 g.

23 g Na is 1 mol

6.9 g Na is ? mol

¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯

?=0.3 mol

4. Find mass of 0.2 mol P4 . (P=31)

Solution:

Molecular mass of P4 = 4.31 =124 g

1 mol P4 is 124 g

0.2 mol P4 is ? mol

¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯

?= 24.8 g

8.4: Volumetric Analysis

Volumetric analysis is a widely-used quantitative analytical method. As the name implies,

this method involves the measurement of volume of a solution of known concentration which
is used to determine the concentration of the analyte.

This is also called titrimetric analysis or titration because volume is an important factor in
titration. It’s a laboratory method of quantitative chemical analysis which is used to
determine the unknown concentration of an analyte. Titration is a volumetric analysis
because it’s based on the measurement of volumes.

One standard solution is used which is solution of a reagent, also called titrant or titrator. A
known volume of titrant reacts with a solution of analyte or titrand to determine its
concentration. Thus, the process involves measuring the volumes of two solutions which
react to each other. The basic principles of volumetric analysis are given as below:

1. The one solution to be analyzed contains an unknown amount of chemicals.

142
 2. The reagent of known concentration reacts with chemical of unknown amount in the
presence of an indicator to show the end-point. This is the point which shows the
completion of the reaction.
3. The volumes are measured by a titration which completes the reaction between
reagent and solution.
4. The volume and concentration of reagent used in the titration give the amount of
reagent in moles.
5. The amount of unknown chemical in the measured volume of solution is calculated by
using the mole ratio of the equation.
6. The amount of unknown chemical in the original sample is calculated by the amount
of unknown chemical in the measured volume.

Volumetric analysis example involving balancing of equations

Question 1: Calculate the concentration of HCl acid if 50ml of HCl is required to neutralize
25ml of 1.00M NaOH in acid base titration.

Solution:
HCl + NaOH -> NaCl + H2O in this chemical reaction the molar ratio is 1:1 between
HCl and NaOH. So moles of HCl = moles of NaOH
[Molarity = moles/volume]
MHCl x volume of HCl = MNaOH x volume of NaOH
Thus,

MHCl = (25.00ml×1.00M)/50.00ml

MHCl = 0.50 M HCl

So the concentration of HCl is 0.50 M.

143
Lecture 9
Gases, liquids and solids
Properties and comparison
Structures of solids
Kinetic theory of matter
Gas Laws and ideal gas equation
Gay Lusaac’s theory

144
 9.1 Gases, liquids and solids

A Molecular Comparison of Gases, Liquids, and Solids

Solids, liquids, gases, and plasmas: these words should be quite familiar to you because they
are the four phases of matter, which are simply the different forms matter can take on. The
physical properties of a substance depends upon its physical state. Water vapor, liquid water
and ice all have the same chemical properties, but their physical properties are considerably
different. In general Covalent bonds determine: molecular shape, bond energies, chemical
properties, while intermolecular forces (non-covalent bonds) influence the physical
properties of liquids and solids. The kinetic molecular theory of gases gives a reasonably
accurate description of the behavior of gases. A similar model can be applied to liquids, but it
must take into account the nonzero volumes of particles and the presence of strong
intermolecular attractive forces.

A Description of Gasses, Liquids, and Solids

The state of a substance depends on the balance between the kinetic energy of the individual
particles (molecules or atoms) and the intermolecular forces. The kinetic energy keeps the
molecules apart and moving around, and is a function of the temperature of the substance and
the intermolecular forces try to draw the particles together.

Gasses are very sensitive to temperatures and pressure. However, these also affect liquids and
solids too. Heating and cooling can change the kinetic energy of the particles in a substance,
and so, we can change the physical state of a substance by heating or cooling it. Increasing
the pressure on a substance forces the molecules closer together, which increases the strength
of intermolecular forces.

Note

• Cooling a gas may change the state to a liquid

• Cooling a liquid may change the state to a solid
• Increasing the pressure on a gas may change the state to a liquid
• Increasing the pressure on a liquid may change the state to a solid

145
Below is an overview of the general properties of the three different phases of matter.

Properties of Gases

• A collection of widely separated molecules

• The kinetic energy of the molecules is greater than any attractive forces between the
molecules
• The lack of any significant attractive force between molecules allows a gas to expand
to fill its container
• If attractive forces become large enough, then the gases exhibit non-ideal behavior

Properties of Liquids

• The intermolecular attractive forces are strong enough to hold molecules close
together
• Liquids are more dense and less compressible than gasses
• Liquids have a definite volume, independent of the size and shape of their container
• The attractive forces are not strong enough, however, to keep neighboring molecules
in a fixed position and molecules are free to move past or slide over one another

Thus, liquids can be poured and assume the shape of their containers

Properties of Solids

• The intermolecular forces between neighboring molecules are strong enough to keep
them locked in position
• Solids (like liquids) are not very compressible due to the lack of space between
molecules
• If the molecules in a solid adopt a highly ordered packing arrangement, the structures
are said to be crystalline

Due to the strong intermolecular forces between neighboring molecules, solids are rigid

Note

Gases have weaker intermolecular forces than liquids and liquids have weaker intermolecular
forces than solids.

Plasmas are ionized gases, and in their natural form are uncommon on Earth. You've seen
them as man-made things, like neon signs and fluorescent light bulbs. But in the rest of the
universe, plasma is actually the most common phase of matter! Most stars are plasma, as are
the northern lights you see around the Polar Regions. Plasma only exists under certain
conditions though.

146
Structure of Solid

Classification of solids

Solids are classified into categories:

• Amorphous solids
• Crystalline solids

The two types of solids have different characteristics.

• Amorphous Solids. An amorphous solid is a substance whose constituents do not

possess an orderly arrangement. Important examples of amorphous solids are glass
and plastics. Although amorphous solids consist of microcrystalline substance but the
orderly arrangement is restricted to very short distances. These distances are of the
same order of magnitude as the interatomic distances.
• Crystalline Solids. A crystalline solid is a substance whose constituents possess an
orderly arrangement in a definite geometric pattern. Some very common examples of
crystalline substances are sodium chloride, sugar and diamond. The main
characteristics of crystalline substances are:
1. Orderly arrangement. The constituent units of crystalline solids are arranged
in an orderly fashion which repeats itself over very long distances as compared
to interatomic distances. The arrangement of bricks in a wall can be
considered as an example. The arrangement is so well defined that the entire
pattern can be repeated provided the arrangement of a few atoms is known.
2. Crystals are always bounded by plane faces.
3. The faces of crystals always meet at some fixed angles

For any particular substances the angle between corresponding pair of faces is always the
same in all crystals. Different crystals of the same substance may sometimes appear to be
different from outside, (either due to different rate of growth by different faces or due to
some damage to the corners or edges) but the interfacial angle is always the same. For
example, sodium chloride grows from water solution as cubes but from 15% aqueous urea as
an octahedron. Two crystals of a single substance with the same lattice but different shapes
are said to be of different habit. On habit modification the relative areas of different faces
change but the angles between such faces remain constant.

4. Crystalline solids exhibit anisotropy in many of their properties.

It means all those properties which depend upon direction or angular
orientation of crystals. These show different behavior in non-parallel
directions. One such consequence of anisotropy is the phenomenon of
cleavage. In crystals the splitting is easier in some directions than others. For
example, in a crystal of sodium chloride cleavage can only be achieved along

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 planes parallel to cube faces. Any attempt to cleave such a crystal along any
arbitrary plane will shatter it.
5. The transition from the solid to liquid (i.e. melting point) for crystalline solids
is sharp and distinct. An amorphous substance, on the other hand, has no
sharp melting point. The transition from solid to liquid in an amorphous solid
does not take place at a define point but extends over a long range. The
absence of sharp melting point suggests that most of amorphous solids may be
best thought of as liquids.
6. Crystalline solids exhibit definite heats of fusion.

Kinetic Theory of Matter by Ron Kurtus (revised 29 December 2017)

The Kinetic Theory of Matter states that matter is composed of a large number of small
particles—individual atoms or molecules—that are in constant motion. This theory is also
called the Kinetic-Molecular Theory of Matter and the Kinetic Theory of Gases.

By making some simple assumptions, such as the idea that matter is made of widely spaced
particles in constant motion, the theory helps to explain the behavior of matter.

Questions you may have include:

• What does matter consist of?

• How close are the particles?
• How much do particles move?

Matter consists of small particles

The first assumption in this theory is that matter consists of a large number a very small
particles—either individual atoms or molecules.

All matter (solid, liquid, and gas) is made up of tiny particles called atoms, or atoms that are
joined to form molecules.

Large separation between particles

The next assumption concerns the separation of the particles.

In a gas, the separation between particles is very large compared to their size, such that there
are no attractive or repulsive forces between the molecules.

In a liquid, the particles are still far apart, but now they are close enough that attractive forces
confine the material to the shape of its container.

In a solid, the particles are so close that the forces of attraction confine the material to a
specific shape.

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Particles are in constant motion

Another assumption is that each particle is in constant motion.

In gases, the movement of the particles is assumed to be random and free.

In liquids, the movement is somewhat constrained by the volume of the liquid.

In solids, the motion of the particles is severely constrained to a small area, in order for the
solid to maintain its shape.

The velocity of each particle determines its kinetic energy. There is an exchange or transfer
of energy between particles—both atoms and molecules—during a collision between them.

Summary

The Kinetic Theory of Matter states that matter is composed of a large number a small
particles that are in constant motion. It also assumes that particles are small and widely
separated. They collide and exchange energy. The theory helps explain the flow or transfer of
heat and the relationship between pressure, temperature and volume properties of gases.

9.2 Gas Laws and ideal gas equation

Many chemists had dreamed of having an equation that describes relation of a gas molecule
to its environment such as pressure or temperature. However, they had encountered many
difficulties because of the fact that there always are other affecting factors such as
intermolecular forces. Despite this fact, chemists came up with a simple gas equation to study
gas behavior while putting a blind eye to minor factors.

When dealing with gas, a famous equation was used to relate all of the factors needed in
order to solve a gas problem. This equation is known as the Ideal Gas Equation. As we have
always known, anything ideal does not exist. In this issue, two well-known assumptions
should have been made beforehand:

1. The particles have no forces acting among them, and

2. These particles do not take up any space, meaning their atomic volume is completely
ignored.

An ideal gas is a hypothetical gas dreamed by chemists and students because it would be
much easier if things like intermolecular forces do not exist to complicate the simple Ideal
Gas Law. Ideal gases are essentially point masses moving in constant, random, straight-line
motion. Its behavior is described by the assumptions listed in the Kinetic-Molecular Theory
of Gases. This definition of an ideal gas contrasts with the Non-Ideal Gas definition, because
this equation represents how gas actually behaves in reality. For now, let us focus on the Ideal

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Gas. In order for a gas to be ideal, its behavior must follow the Kinetic-Molecular Theory
whereas the Non-Ideal Gases will deviate from this theory due to real world conditions.

The Ideal Gas Equation

Before we look at the Ideal Gas Equation, let us state the four gas variables and one
constant for a better understanding. The four gas variables are: pressure (P), volume (V),
number of mole of gas (n), and temperature (T). Lastly, the constant in the equation shown
below is R, known as the gas constant, which will be discussed in depth further later:

PV=nRT

Values of R
0.082057 L atm mol-1 K-1
62.364 L Torr mol-1 K-1
8.3145 m3 Pa mol-1 K-1
8.3145 J mol-1 K-1*

Another way to describe an ideal gas is to describe it in mathematically. Consider the

following equation:

PV/nRT=1

The term PV/nRT is also called the compression factor and is a measure of the ideality of the
gas. An ideal gas will always equal 1 when plugged into this equation. The greater it deviates
from the number 1, the more it will behave like a real gas rather than an ideal. A few things
should always be kept in mind when working with this equation, as you may find it extremely
helpful when checking your answer after working out a gas problem.

• Pressure is directly proportional to number of molecule and temperature. (Since P is

on the opposite side of the equation to n and T)
• Pressure, however, is indirectly proportional to volume. (Since P is on the same side
of the equation with V)

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Example

Simple Gas Laws

The Ideal Gas Law is simply the combination of all Simple Gas Laws (Boyle's Law, Charles'
Law, and Avogadro's Law), and so learning this one means that you have learned them all.
The Simple Gas Laws can always be derived from the Ideal Gas equation.

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Boyle's Law

Boyle’s Law describes the inverse proportional relationship between pressure and volume at
a constant temperature and a fixed amount of gas. This law came from a manipulation of the
Ideal Gas Law.

P∝1/V

Or expressed from two pressure/volume points:

P1V1=P2V2

This equation would be ideal when working with problem asking for the initial or final value
of pressure or volume of a certain gas when one of the two factor is missing.

Charles's Law

Charles's Law describes the directly proportional relationship between the volume and
temperature (in Kelvin) of a fixed amount of gas, when the pressure is held constant.

V∝T

Or express from two volume/temperature points:

V1T1=V2T2

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This equation can be used to solve for initial or final value of volume or temperature under
the given condition that pressure and the number of mole of the gas stay the same.

Amontons's Law

Given a constant number of mole of a gas and an unchanged volume, pressure is directly
proportional to temperature.

P∝T

Or expressed as two pressure/temperature points:

P1T1=P2T2

Avogadro's Law

Volume of a gas is directly proportional to the amount of gas at a constant temperature and
pressure.

V∝n

Or expressed as a two volume/number points:

V1n1=V2n2

Avogadro's Law can apply well to problems using Standard Temperature and Pressure,
because of a set amount of pressure and temperature.

Avogadro’s Theory (Further explanation)

Avogadro’s law, a statement that under the same conditions of temperature and pressure,
equal volumes of different gases contain an equal number of molecules. Avogadro's gas law
states the volume of a gas is proportional to the number of moles of gas present when the
temperature and pressure are held constant. Avogadro's law is also called Avogadro's
principle or Avogadro's hypothesis. This empirical relation can be derived from the kinetic
theory of gases under the assumption of a perfect (ideal) gas. The law is approximately valid
for real gases at sufficiently low pressures and high temperatures.

The specific number of molecules in one gram-mole of a substance, defined as the molecular
weight in grams, is 6.022140857 × 1023, a quantity called Avogadro’s number, or the
Avogadro constant. For example, the molecular weight of oxygen is 32.00, so that one gram-
mole of oxygen has a mass of 32.00 grams and contains 6.022140857 × 1023 molecules.

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The volume occupied by one gram-mole of gas is about 22.4 liters (0.791 cubic foot) at
standard temperature and pressure (0 °C, 1 atmosphere) and is the same for all gases,
according to Avogadro’s law.

The law was first proposed in 1811 by Amedeo Avogadro, a professor of higher physics at
the University of Turin for many years, but it was not generally accepted until after 1858,
when an Italian chemist, Stanislao Cannizzaro, constructed a logical system of chemistry
based on it.

Avogadro's Law Equation

Before you can solve any problem regarding Avogadro's gas law, it's important to review the
equation for this law.

There are a few ways to write this gas law, which is a mathematical relation. It may be stated:

k = V/n

Here, k is a proportionality constant, V is the volume of a gas, and n is the number of moles
of a gas. Avogadro's law also means the ideal gas constant is the same value for all gases, so:

Constant = p1V1/T1n1 = P2V2/T2n2

V1/n1 = V2/n2

V1n2 = V2n1

Where p is pressure of a gas, V is volume, T is temperature, and n is number of moles.

Avogadro's Law Problem

A 6.0 L sample at 25°C and 2.00 atm of pressure contains 0.5 mole of a gas. If an additional
0.25 mole of gas at the same pressure and temperature are added, what is the final total
volume of the gas?

Solution

First, express Avogadro's law by its formula:

Vi/ni = Vf/nf

where
Vi = initial volume
ni = initial number of moles

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Vf = final volume
nf = final number of moles

For this example, Vi = 6.0 L and ni = 0.5 mole. When 0.25 mole is added:

nf = ni + 0.25 mole
nf = 0.5 mole + 0.25 mole
nf = 0.75 mole

The only variable remaining is the final volume.

Vi/ni = Vf/nf

Solve for Vf

Vf = Vinf/ni

Vf = (6.0 L x 0.75 mole)/0.5 mole

Vf = 4.5 L/0.5 Vf = 9 L

Check to see if the answer makes sense. You would expect the volume to increase if more gas
is added. Is the final volume greater than the initial volume? Yes.

Doing this check is useful because it is easy to put the initial number of moles in the
numerator and the final number of moles in the denominator. If this had happened, the final
volume answer would have been smaller than the initial volume.

Thus, the final volume of the gas is 9.0

Standard Temperature and Pressure (STP)

Standard condition of temperature and pressure is known as STP. Two things you should
know about this is listed below.

• The universal value of STP is 1atm (pressure) and 0o C. Note that this form
specifically stated 0o C degree, not 273 Kelvin, even though you will have to convert
into Kelvin when plugging this value into the Ideal Gas equation or any of the simple
gas equations.
• In STP, 1 mole of gas will take up 22.4 L of the volume of the container.

Gay Lussac’s Theory

This relationship between temperature and pressure is known as Gay-Lussac's law. It states
that if the volume of a container is held constant as the temperature of a gas increases, the

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pressure inside the container will also increase. As with the other gas laws, this one can be
represented in the form of an equation:

P1/T1 = P2/T2

P1 = initial pressure

T1 = initial absolute temperature

P2 = final pressure

T2 = final absolute temperature

It is extremely important to remember the temperatures are absolute temperatures measured

in Kelvin, NOT °C or °F.

Gay-Lussac's Law Example

A 20-liter cylinder contains 6 atmospheres (atm) of gas at 27 C. What would the pressure of
the gas be if the gas was heated to 77 C?

To solve the problem, just work through the following steps:

The cylinder's volume remains unchanged while the gas is heated so Gay-Lussac's gas law
applies. Gay-Lussac's gas law can be expressed as:

Pi/Ti = Pf/Tf

where
Pi and Ti are the initial pressure and absolute temperatures
Pf and Tf are the final pressure and absolute temperature

First, convert the temperatures to absolute temperatures.

Ti = 27 C = 27 + 273 K = 300 K
Tf = 77 C = 77 + 273 K = 350 K

Use these values in Gay-Lussac's equation and solve for Pf.

Pf = PiTf/Ti
Pf = (6 atm).(350K)/(300 K)
Pf = 7 atm

The answer you derive would be:

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The pressure will increase to 7 atm after heating the gas from 27 C to 77 C.

Boyle's Law, Charles' Law, and Avogadro’s Law, Gay-Lussac’s Law and Amontons's Law
are given under certain conditions so directly combining them will not work. Through
advanced mathematics, the properties of the three simple gas laws will give you the Ideal Gas
Equation.

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Lecture 10
Energetics
Heats of reactions.
Hess’s law and Born-Haber cycle.
Lattice energy

158
 10.1: Chemical Energetics
In Inorganic Chemistry you have learned that the material world is made up of some 90
natural occurring chemical elements, some more abundant than others. They combine with
each other to make up compounds, mixtures, solutions, colloids, aggregates, and composite
materials. The atoms are made up of tiny nuclei and surround by electrons.

The material world is constantly changing. The changes give rise to all sorts of phenomena,
including light, thunder, flood, storms, and heat observed in the weather. Did you ever ask
yourself what make the material change? Well, former scientists have analyzed the question,
and they have provided a simple answer to this. Energy causes all the changes. However, the
concept of energy and how it behave are very difficult to master. On the other hand, once you
have mastered it, you will appreciate the simplicity and realize the beauty of this concept.

What is Chemical Energetics?

Chemical energetics is the study of chemical changes caused by energy. Chemical
energetics discusses both thermal dynamics and kinetics or reactions.

Thermodynamics discusses changes based on amounts of energy. Since energy is conserved,

energy transferred into a system is called internal energy. The amount of energy in a
reaction remains the same regardless whether the reaction (or change) takes place in one or
several steps. This principle is illustrated by the Hess's law, the application of which gives the
estimate of energy in a process. Measurements of energy is called calorimetry, and they can
be measured under constant volume or constant pressure. A system tends to minimize its
Gibb's free energy, G, and such a tendency leads to the concept of chemical equilibria. These
topics require lengthy discussion, and each is a sub-unit of study.

Chemical Kinetics which deals with the rate of reactions. A good example to illustrate the
two factors is the existence of diamond and graphite. At room temperature and pressure,
thermodynamics indicates that the stable form of carbon is graphite. From a thermodynamic
point of view, diamond should convert to graphite. But the reaction rate (kinetics) is so slow
that there is no detectable change.

The temperature dependence associated with chemical kinetics is discussed in terms of

activation energy, which is often perceived as the energy barrier that has to be overcome in
order for a reaction to proceed.

However, kinetics of chemical reaction also deals with rate laws, elementary steps, and
mechanisms of reactions.

Heats of reactions

The Heat of Reaction (also known and Enthalpy of Reaction) is the change in the enthalpy of
a chemical reaction that occurs at a constant pressure. It is a thermodynamic unit of
measurement useful for calculating the amount of energy per mole either released or
produced in a reaction. Since enthalpy is derived from pressure, volume, and internal energy,
all of which are state functions, enthalpy is also a state function.

ΔH, or the change in enthalpy arose as a unit of measurement meant to calculate the change
in energy of a system when it became too difficult to find the ΔU, or change in the internal
energy of a system, by simultaneously measure the amount of heat and work

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exchanged. Given a constant pressure, the change in enthalpy can be measured as ΔH=q (see
enthalpy for a more detailed explanation).

The notation ΔHº or ΔHºrxn then arises to explain the precise temperature and pressure of the
heat of reaction ΔH. The standard enthalpy of reaction is symbolized by ΔHº or ΔHºrxn and
can take on both positive and negative values. The units for ΔHº are kilojoules per mole, or
kj/mol.

ΔH and ΔHºrxn

• Δ = represents the change in the enthalpy; (ΔHproducts -ΔHreactants)

o a positive value indicates the products have greater enthalpy, or that it is an
endothermic reaction (heat is required)
o a negative value indicates the reactants have greater enthalpy, or that it is an
exothermic reaction (heat is produced)
• º = signifies that the reaction is a standard enthalpy change, and occurs at a preset
pressure/temperature
• rxn = denotes that this change is the enthalpy of reaction

The Standard State: The standard state of a solid or liquid is the pure substance at a pressure
of 1 bar (105 Pa) and at a relevant temperature.

The ΔHºrxn is the standard heat of reaction or standard enthalpy of reaction, and like ΔH also
measures the enthalpy of a reaction. However, ΔHºrxn takes place under "standard"
conditions, meaning that the reaction takes place at 25º C and 1 atm. The benefit of a
measuring ΔH under standard conditions lies in the ability to relate one value of ΔHº to
another, since they occur under the same conditions.

Thus, Standard enthalpy of formation is the enthalpy change when 1 mole of a compound is
formed from its elements under standard conditions while Standard enthalpy of reaction is
the enthalpy change when the amounts of reactants given in reaction equation react under
standard conditions to give products in the standard conditions.

Types of Enthalpies of Reactions

One way to report the heat absorbed or released would be to compile a massive set of
reference tables that list the enthalpy changes for all possible chemical reactions, which
would require an incredible amount of effort. Fortunately, Hess’s law allows us to calculate
the enthalpy change for virtually any conceivable chemical reaction using a relatively small
set of tabulated data, such as the following:

• Enthalpy of combustion (ΔHcomb) - The change in enthalpy that occurs during a

combustion reaction. Enthalpy changes have been measured for the combustion of
virtually any substance that will burn in oxygen; these values are usually reported as
the enthalpy of combustion per mole of substance.
• Enthalpy of fusion (ΔHfus) - The enthalpy change that accompanies the melting
(fusion) of 1 mol of a substance. The enthalpy change that accompanies the melting,

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 or fusion, of 1 mol of a substance; these values have been measured for almost all the
elements and for most simple compounds.
• Enthalpy of vaporization (ΔHvap) - The enthalpy change that accompanies the
vaporization of 1 mol of a substance. The enthalpy change that accompanies the
vaporization of 1 mol of a substance; these values have also been measured for nearly
all the elements and for most volatile compounds.
• Enthalpy of solution (ΔHsoln) - The change in enthalpy that occurs when a specified
amount of solute dissolves in a given quantity of solvent. The enthalpy change when a
specified amount of solute dissolves in a given quantity of solvent.
• The enthalpy of reaction (heat of reaction) for a neutralization reaction is known as
the enthalpy of neutralization (heat of neutralization).

Enthalpy of reaction (heat of reaction) can be measured experimentally using a calorimeter.

Hess’s law

Hess's Law of Constant Heat Summation (or just Hess's Law) states that regardless of the
multiple stages or steps of a reaction, the total enthalpy change for the reaction is the sum of
all changes. This law is a manifestation that enthalpy is a state function.

Hess's Law is named after Russian Chemist and Doctor Germain Hess. Hess helped formulate
the early principles of thermochemistry. His most famous paper, which was published in
1840, included his law on thermochemistry. Hess's law is due to enthalpy being a state
function, which allows us to calculate the overall change in enthalpy by simply summing up
the changes for each step of the way, until product is formed. All steps have to proceed at the
same temperature and the equations for the individual steps must balance out. The principle
underlying Hess's law does not just apply to Enthalpy and can be used to calculate other state
functions like changes in Gibbs' Energy and Entropy.

Definition: Hess's Law

The heat of any reaction ΔH∘f for a specific reaction is equal to the sum of the heats of
reaction for any set of reactions which in sum are equivalent to the overall reaction.

Lattice energy and Born-Haber cycle

Ionic solids tend to be very stable compounds. The enthalpies of formation of the ionic
molecules cannot alone account for this stability. These compounds have an additional
stability due to the lattice energy of the solid structure. However, lattice energy cannot be
directly measured. The Born-Haber cycle allows us to understand and determine the lattice
energies of ionic solids.

This topic will introduce the idea of lattice energy, as well as one process that allows us to
calculate it: the Born-Haber Cycle. In order to use the Born-Haber Cycle, there are several
concepts that we must understand first.

Lattice Energy

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Lattice Energy is a type of potential energy that may be defined in two ways. In one
definition, the lattice energy is the energy required to break apart an ionic solid and convert
its component atoms into gaseous ions. This definition causes the value for the lattice energy
to always be positive, since this will always be an endothermic reaction. The other definition
says that lattice energy is the reverse process, meaning it is the energy released when gaseous
ions bind to form an ionic solid. As implied in the definition, this process will always be
exothermic, and thus the value for lattice energy will be negative. Its values are usually
expressed with the units kJ/mol.

Lattice Energy is used to explain the stability of ionic solids. Some might expect such an
ordered structure to be less stable because the entropy of the system would be low. However,
the crystalline structure allows each ion to interact with multiple oppositely charge ions,
which causes a highly favorable change in the enthalpy of the system. A lot of energy is
released as the oppositely charged ions interact. It is this that causes ionic solids to have such
high melting and boiling points. Some require such high temperatures that they decompose
before they can reach a melting and/or boiling point.

Born-Haber Cycle

There are several important concept to understand before the Born-Haber Cycle can be
applied to determine the lattice energy of an ionic solid; ionization energy, electron affinity,
dissociation energy, sublimation energy, heat of formation, and Hess's Law.

• Ionization Energy is the energy required to remove an electron from a neutral atom
or an ion. This process always requires an input of energy, and thus will always have
a positive value. In general, ionization energy increases across the periodic table from
left to right, and decreases from top to bottom. There are some exceptions, usually
due to the stability of half-filled and completely filled orbitals.
• Electron Affinity is the energy released when an electron is added to a neutral atom
or an ion. Usually, energy released would have a negative value, but due to the
definition of electron affinity, it is written as a positive value in most tables.
Therefore, when used in calculating the lattice energy, we must remember to subtract
the electron affinity, not add it. In general, electron affinity increases from left to right
across the periodic table and decreases from top to bottom.
• Dissociation energy is the energy required to break apart a compound. The
dissociation of a compound is always an endothermic process, meaning it will always
require an input of energy. Therefore, the change in energy is always positive. The
magnitude of the dissociation energy depends on the electronegativity of the atoms
involved.
• Sublimation energy is the energy required to cause a change of phase from solid to
gas, bypassing the liquid phase. This is an input of energy, and thus has a positive
value. It may also be referred to as the energy of atomization.
• The heat of formation is the change in energy when forming a compound from its
elements. This may be positive or negative, depending on the atoms involved and how
they interact.
• Hess's Law states that the overall change in energy of a process can be determined by
breaking the process down into steps, then adding the changes in energy of each step.
The Born-Haber Cycle is essentially Hess's Law applied to an ionic solid.

Using the Born-Haber Cycle

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The values used in the Born-Haber Cycle are all predetermined changes in enthalpy for the
processes described in the section above. Hess' Law allows us to add or subtract these values,
which allows us to determine the lattice energy.

Step 1

Determine the energy of the metal and nonmetal in their elemental forms. (Elements in their
natural state have an energy level of zero.) Subtract from this the heat of formation of the
ionic solid that would be formed from combining these elements in the appropriate ration.
This is the energy of the ionic solid, and will be used at the end of the process to determine
the lattice energy.

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Step 2

The Born-Haber Cycle requires that the elements involved in the reaction are in their gaseous
forms. Add the changes in enthalpy to turn one of the elements into its gaseous state, and then
do the same for the other element.

Step 3

Metals exist in nature as single atoms and thus no dissociation energy needs to be added for
this element. However, many nonmetals will exist as polyatomic species. For example, Cl
exists as Cl2 in its elemental state. The energy required to change Cl2 into 2Cl atoms must be
added to the value obtained in Step 2.

Step 4

Both the metal and nonmetal now need to be changed into their ionic forms, as they would
exist in the ionic solid. To do this, the ionization energy of the metal will be added to the
value from Step 3. Next, the electron affinity of the nonmetal will be subtracted from the
previous value. It is subtracted because it is a release of energy associated with the addition
of an electron.

*This is a common error due to confusion caused by the definition of electron affinity, so be
careful when doing this calculation.

Step 5

Now the metal and nonmetal will be combined to form the ionic solid. This will cause a
release of energy, which is called the lattice energy. The value for the lattice energy is the
difference between the value from Step 1 and the value from Step 4.

The diagram below is another representation of the Born-Haber Cycle.

Equation

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The Born-Haber Cycle can be reduced to a single equation:

Heat of formation= Heat of atomization+ Dissociation energy+ (sum of Ionization energies)+

(sum of Electron affinities)+ Lattice energy

*Note: In this general equation, the electron affinity is added. However, when plugging in a
value, determine whether energy is released (exothermic reaction) or absorbed (endothermic
reaction) for each electron affinity. If energy is released, put a negative sign in front of the
value; if energy is absorbed, the value should be positive.

Rearrangement to solve for lattice energy gives the equation:

Lattice energy= Heat of formation- Heat of atomization - Dissociation energy - (sum of

Ionization energies) - (sum of Electron Affinities)

Example

165
Lecture 11:
Equilibrium
Equilibrium constant
LeChateliar’s principle
Solubility product

166
 11.1: Chemical Equilibrium

Hydrogen and iodine gases react to form hydrogen iodide according to the following
reaction:

H2(g) + (g) ⇌ 2HI(g)

Forward reaction: H2(g) + I2(g) → 2HI(g)
Reverse reaction: 2HI(g) → H2(g) + I2(g)

When the rates of the forward and reverse reactions have become equal to one another, the
reaction has achieved a state of balance. Chemical equilibrium is the state of a system in
which the rate of the forward reaction is equal to the rate of the reverse reaction.

Conditions for Equilibrium

It may be tempting to think that once equilibrium has been reached, the reaction stops.
Chemical equilibrium is a dynamic process. The forward and reverse reactions continue to
occur even after equilibrium has been reached. However, because the rates of the reactions
are the same, there is no change in the relative concentrations of reactants and products for a
reaction that is at equilibrium. The conditions and properties of a system at equilibrium are
summarized below.

1. The system must be closed, meaning no substances can enter or leave the system.
2. Equilibrium is a dynamic process. Even though we don't necessarily see the reactions,
both the forward and reverse reactions are taking place.
3. The rates of the forward and reverse reactions must be equal.
4. The amount of reactants and products do not have to be equal. However, after
equilibrium is attained, the amounts of reactants and products will be constant.

The description of equilibrium in this concept refers primarily to equilibrium between

reactants and products in a chemical reaction. Other types of equilibrium include phase
equilibrium and solution equilibrium. A phase equilibrium occurs when a substance is in
equilibrium between two states. For example, a stoppered flask of water attains equilibrium
when the rate of evaporation is equal to the rate of condensation. A solution equilibrium
occurs when a solid substance is in a saturated solution. At this point, the rate of dissolution
is equal to the rate of recrystallization. Although these are all different types of
transformations, most of the rules regarding equilibrium apply to any situation in which a
process occurs reversibly.

Equilibrium Constant

Consider the hypothetical reversible reaction in which reactants A and B react to form
products C and D. This equilibrium can be shown below, where the lower case letters
represent the coefficients of each substance.

aA + bB ⇌ cC + dD

As we have established, the rates of the forward and reverse reactions are the same at
equilibrium, and so the concentrations of all of the substances are constant. Since that is the

167
case, it stands to reason that a ratio of the concentrations for any given reaction at equilibrium
maintains a constant value. The equilibrium constant (Keq) is the ratio of the mathematical
product of the concentrations of the products of a reaction to the mathematical product of the
concentrations of the reactants of the reaction. Each concentration is raised to the power of its
coefficient in the balanced chemical equation. For the general reaction above, the equilibrium
constant expression is written as follows:

The concentrations of each substance, indicated by the square brackets around the formula,
are measured in molarity units (mol/L). The value of the equilibrium constant for any
reaction is only determined by experiment. As detailed in the previous section, the position of
equilibrium for a given reaction does not depend on the starting concentrations and so the
value of the equilibrium constant is truly constant. It does, however, depend on the
temperature of the reaction. This is because equilibrium is defined as a condition resulting
from the rates of forward and reverse reactions being equal. If the temperature changes, the
corresponding change in those reaction rates will alter the equilibrium constant. For any
reaction in which a Keq is given, the temperature should be specified.

Example

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 11.2 Le Châtelier's Principle

Chemical equilibrium was studied by French chemist Henri Le Châtelier (1850 - 1936) and
his description of how a system responds to a stress to equilibrium has become known as Le
Châtelier's principle: When a chemical system that is at equilibrium is disturbed by a stress,
the system will respond in order to relieve the stress. Stresses to a chemical system involve
changes in the concentration of reactants or products, changes in the temperature of the
system, or changes in the pressure of the system. Le Chatelier's principle. Le Chatlier's
principle (also known as "Chatelier's principle" or "The Equilibrium Law") states that
when a system experiences a disturbance (such as concentration, temperature, or pressure
changes), it will respond to restore a new equilibrium state.

The law of mass action is one example of Le Chatelier's principle. The law of mass action
states that the rate at which substance reacts is proportional to its active mass and the rate of
chemical reaction is proportional to the product of the active masses of the reactants.

When the forward reaction is favored, the concentrations of products increase, while the
concentrations of reactants decrease. When the reverse reaction is favored, the concentrations
of products decrease, while the concentrations of reactants increase.

Effect of Concentration

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A change in concentration of one of the substances in an equilibrium system typically
involves either the addition or the removal of one of the reactants or products. Consider the
Haber-Bosch process for the industrial production of ammonia from nitrogen and hydrogen
gases.

N2 (g) + 3H2 (g) ⇌ 2NH3(g)

If the concentration of one substance in a system is increased, the system will respond by
favoring the reaction that removes that substance. When more N2 is added, the forward
reaction will be favored because the forward reaction uses up N2 and converts it to NH3. The
forward reaction speeds up temporarily as a result of the addition of a reactant. The position
of equilibrium shifts as more NH3 is produced. The concentration of NH3 increases, while
the concentrations of N2 and H2 decrease. After some time passes, equilibrium is
reestablished with new concentrations of all three substances. As can be seen in the figure
below, if more N2 is added, a new equilibrium is achieved by the system. The new
concentration of NH3 is higher because of the favoring of the forward reaction. The new
concentration of the H2 is lower. The concentration of N2 is higher than in the original
equilibrium, but went down slightly following the addition of the N2 that disturbed the
original equilibrium. By responding in this way, the value of the equilibrium constant for the
reaction, Keq, does not change as a result of the stress to the system.

If more NH3 were added, the reverse reaction would be favored. This "favoring" of a reaction
means temporarily speeding up the reaction in that direction until equilibrium is
reestablished. Recall that once equilibrium is reestablished, the rates of the forward and
reverse reactions are again equal. The addition of NH3 would result in increased formation of
the reactants, N2 and H2.
An equilibrium can also be disrupted by the removal of one of the substances. If the
concentration of a substance is decreased, the system will respond by favoring the reaction
that replaces that substance. In the industrial Haber-Bosch process, NH3 is removed from the
equilibrium system as the reaction proceeds. As a result, the forward reaction is favored so
that more NH3 will be produced. The concentrations of N2 and H2 decrease. Continued
removal of NH3 will eventually force the reaction to go to completion until all of the
reactants are used up. If either N2 or H2 were removed from the equilibrium system, the
reverse reaction would be favored and the concentration of NH3 would decrease.

Effect of temperature

Le Châtelier's principle states that a change in temperature, pressure, or concentration of

reactants in an equilibrated system will stimulate a response that partially off-sets the change
to establish a new equilibrium. In the case of changing temperature, adding or removing of
heat shifts the equilibrium.

• Raising the temperature favors the reverse reaction (endothermic)

• Lowering the temperature favors the forward reaction (exothermic)

Using Le Chatelier's Principle with a change of pressure

This only applies to reactions involving gases:

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What would happen if you changed the conditions by increasing the pressure?

According to Le Chatelier, the position of equilibrium will move in such a way as to

counteract the change. That means that the position of equilibrium will move so that the
pressure is reduced again.

Pressure is caused by gas molecules hitting the sides of their container. The more molecules
you have in the container, the higher the pressure will be. The system can reduce the pressure
by reacting in such a way as to produce fewer molecules.

In this case, there are 3 molecules on the left-hand side of the equation, but only 2 on the
right. By forming more C and D, the system causes the pressure to reduce.

Increasing the pressure on a gas reaction shifts the position of equilibrium towards the side
with fewer molecules.

What would happen if you changed the conditions by decreasing the pressure?

The equilibrium will move in such a way that the pressure increases again. It can do that by
producing more molecules. In this case, the position of equilibrium will move towards the
left-hand side of the reaction.

What happens if there are the same number of molecules on both sides of the equilibrium
reaction?

In this case, increasing the pressure has no effect whatsoever on the position of the
equilibrium. Because you have the same numbers of molecules on both sides, the equilibrium
can't move in any way that will reduce the pressure again.

11.3 Solubility Product

Ksp - Solubility product constant definition

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Solubility product constant is simplified equilibrium constant (Ksp) defined for equilibrium
between a solids and its respective ions in a solution. Its value indicates the degree to which a
compound dissociates in water. The higher the solubility product constant, the more soluble
the compound.

The Ksp expression for a salt is the product of the concentrations of the ions, with each
concentration raised to a power equal to the coefficient of that ion in the balanced equation
for the solubility equilibrium.

Solubility product constants are used to describe saturated solutions of ionic compounds of
relatively low solubility. A saturated solution is in a state of dynamic equilibrium between the
dissolved, dissociated, ionic compound and the undissolved solid. As for everu solution, at
equilibrium in given conditions we can write an expression like the one below for Silver
chloride:

Where [Ag+] and [Cl-] represent concentrations of ions of Ag+ and Cl- and [AgCl] is a value
representing an amount of moles in a litre of solid AgCl. [AgCl] is a constant, therefore,
writing a following equation:

Kc x [AgCl] = [Ag+][Cl-]

We can notice that product of equilibrium concentration of Ag+ and Cl- is equal to a constant.
This constant is called solubility product constant or Ksp

Ksp = [Ag+][Cl-]

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Lecture 12
Reaction Rates
Factors affecting reaction rates
Rate laws and Order of reactions

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12.1: Reaction Rates

The reaction rate or rate of reaction is the speed at which reactants are converted into
products. Chemical reaction rates are the rates of change in concentrations or amounts of
either reactants or products. Chemical kinetics is the part of physical chemistry that studies
reaction rates.

Further definition: Chemical kinetics is the study and discussion of chemical reactions with
respect to reaction rates, effect of various variables, re-arrangement of atoms, formation of
intermediates etc. By the way, the study of motion is called kinetics, from Greek kinesis,
meaning movement.

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Factors affecting Reaction Rates
Many factors influence rates of chemical reactions, and these are summarized below. Much
more extensive discussion will be given in other pages.

1. Nature of Reactants
Acid-base reactions, formation of salts, and exchange of ions are fast reactions.
Reactions in which large molecules are formed or break apart are usually slow.
Reactions breaking strong covalent bonds are also slow.
2. Temperature
Usually, the higher the temperature, the faster the reaction. The temperature effect is
discussed in terms of activation energy.
3. Concentration Effect
The dependences of reaction rates on concentrations are called rate laws. Rate laws
are expressions of rates in terms of concentrations of reactants. Keep in mind that rate
laws can be in differential forms or integrated forms. They are called differential rate
laws and integrated rate laws. The following is a brief summary of topics regarding
rate laws.
o rate laws: differential and integrated rate laws.
o Integrated rate laws: First Order Reactions
Second Order Reactions

Rate laws apply to homogeneous reactions in which all reactants and products are in
one phase (solution).

4. Heterogeneous reactions: reactants are present in more than one phase.

For heterogeneous reactions, the rates are affected by surface areas.
5. Catalysts: substances used to facilitate reactions
By the nature of the term, catalysts play important roles in chemical reactions.

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176
Note:

Chemical reactions are often classified as zero-order, first-order, second-order, mixed-order,

or higher-order. The general reaction aA + bB → cC + dD is often used in this topic:

• Zero-order in the reactant: there is no effect on the initial rate of reaction

• First-order in the reactant: the initial rate of reaction doubles when the reactant is
doubled
• Second order in the reactant: the initial rate of the reaction quadruples when the
reactant is doubled
• Third order in the reactant: the initial rate of reaction increases eightfold when the
reactant is doubled

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