CHM 101: Introductory Inorganic Chemistry

Ayi A. Ayi
TEXT BOOKS:
1. Understanding Inorganic Chemistry through Problems
and Solutions
2. SIMPLE APPROACH TO GENERAL AND INORGANIC
CHEMISTRY
 OUTLINE
• What is Chemistry
• Scientific method
• Classification and properties of matter
• Pure substances and mixtures
• Physical changes and properties
• States of matter
• Modern Electronic Theory of Atom - Ayi
• Particulate nature of mater -
• Modern Periodic Table and Periodic Properties
• Chemical Bonding
• Shapes of molecules
• Radioactivity
• Types of chemical reactions -
 Matter and its composition
Introduction
• The learning of Chemistry as a course may not be that
difficult as is commonly believed by many people at the
introductory level.
• Chemistry is everywhere in our lives. My understanding of
Chemistry has made me to realize that my mother from her
cooking experience in the kitchen has been a practicing
chemist.
• She knows that oil and water do not mix and that boiling
water left on a burning stove will evaporate.
• She has been applying chemical principles each time she
use baking powder to make bread or cake, squeeze lemon
juice over sliced pears to prevent them from turning brown
or over fish to prevent spoilage.
• The air we breathe, the food we eat, the clothes we wear
and all the materials that surround us in our everyday life
are made up of chemicals.
• Your body is a complex mixture of chemical substances
(65% of which is a chemical compound called water) and
you are kept alive by chemical reactions taking place in
your cells.
• The medical doctors prescribe chemicals as medicines
when we are sick.
• Understanding the chemistry of all these substances and
the chemical reactions involved, allows us to understand
and take control of ourselves and our environment.
•
 What is Chemistry
• Chemistry is the branch of natural science that deals with
synthesis, composition and structure, properties and
applications of matter.
• Synthesis: refers to formation of new (and usually more
complex) substances from simpler ones. It is the operations
required to bring about chemical change and to isolate the
desired products.
• Composition and Structure: define the substances that are
results of chemical change. Structure refers specifically to the
relative arrangements of the atoms in space.
• Properties and Applications of matter: The science of
chemistry developed from observations made about
the nature and behavior of different kinds of matter, is
collectively called the properties of matter.
• Much of chemistry as-a-science is devoted to
understanding the relation between structure and
properties.
• For some purposes it is convenient to distinguish
between chemical properties and physical properties.
• It is through these properties that we experience and
find uses for substances.
•
 Scientific method

• The understanding of the simple as well as complex

chemical processes requires systematic approach to
research- the scientific method, which is a procedure
that can be thought of as a series of steps.
• The development of the modern atomic structure is a
good example of the scientific method.
• The first step while carrying out any investigation is to
identify or define the problem and then collect data by
performing experiments, making observations (careful
attention to details) and recording the data about the
system (the part of the universe under investigation).
• The data obtained in a research study could be
• qualitative,
– consisting of general observations about the system
or
– quantitative,
– comprising numbers obtained by various
measurements of the system.
• In chemistry, we use symbols and equations in
recording measurements and observations.
•
• The next step in scientific method is to
interpret data and formulate hypothesis,
• Hypothesis is a tentative explanation for a set
of observations.
• This step requires insight, imagination and
creativity.
• Hypotheses that survive many experimental
tests of their validity may evolve into theory.
• A theory is a unifying principle that explains a
body of facts and /or those laws based on them.
• A theory is sometimes interpreted through a
model, a simplified version of the system studied.
• Theories and models must also be subjected to
experiment and revised if they are not supported
by experimental results.
•
Steps involved in Scientific method
• Scientific Method therefore consists of the following steps:
• 1) Objective (Problem): statement of purpose, what are
you trying to discover or show?
•
• 2) Hypothesis (Prediction): A proposed explanation for a
problem and a predicted outcome, an “educated guess”
based on research information.
• It is often stated in an “if; then” format.
• For example, if one wishes to determine the effects of
increasing temperature on reaction rate, the hypothesis
might be “If the temperature of the reactants is increased,
the rate of the chemical reaction will increase.”
•
• 3) Experiment (Test): an activity designed to test the
hypothesis.
• This involve two factors namely
– a variable factor – the factor being tested and
– control factors – the other factors that are held constant.
• Example: If you want to test the effects of changing
temperature on the rate of a chemical reaction,
– the variable is temperature (which is controlled by using a
hot plate or bunsen burner) and
– the controls would include the amount of chemicals being
reacted, the identity of the chemicals being reacted, the
surface area, concentration and pressure exerted on the
reacting chemicals.
•
 Scientific method contd.
• 4) Observations (Data):
• what the experimenter senses using the five senses or detects
with the aid of an experimental tool.
– Length, mass, volume, time, temperature, density and pressure are
just a few of the things that can be measured.
– Color and clarity changes are some of the observations that can be
made.
• 5) Analysis (Results):
• organizing data into meaningful groups,
– tables,
– graphs and charts.
• 6) Conclusions the determination of whether
or not the hypothesis or prediction was
correct. The hypothesis may be accepted,
rejected or revised.
• 7) Follow-Up (verification): a repeat of the
experiment with modifications if needed, and
a re-evaluation of the results. Also, answering
one question often leads to new questions.
 Classification and properties of Matter

• Matter is anything that has weight and occupies

space.
• It is made up of atoms bound together to form
molecules and assembled to form larger structures.
• Matter is therefore the stuff that makes the universe;
it is divided into pure substances and mixtures.
• Pure Substances and Mixtures
• A substance is a form of matter with a definite
composition and distinct properties.
• Pure substances may be elements or
compounds.
•
• Element: An element is a substance that consists of
only one kind of atom. It is the fundamental building
block of matter and can not be broken down to simpler
•
substances by physical or chemical means.
• Two or more elements can combine in two different
ways: by physical changes to form mixtures or by
chemical changes to form compounds.
• Physical changes do not involve a change in the
composition or the identity of a substance whereas
chemical change or chemical reaction changes the
composition and the characteristic properties of a
substance
• Compound: A compound is a substance that consists of
atoms of two or more elements chemically bound in fixed
proportions.

• Mixtures: A mixture is a physical combination of two or

more substances with properties related to those of their
components but without definite compositions.

• Mixtures are either homogeneous or heterogeneous. In

homogeneous mixtures (i.e is solution) the composition is
uniform whereas in heterogeneous mixtures, the
composition is not uniform.
•
• Homogeneous mixtures are called SOLUTIONS. Examples
of these mixtures include:
• 1) Aqueous solutions: NaCl (aq) Aqueous means that the
solute (NaCl) is dissolved into WATER.
• This is an example of a SOLUTION. It can not be separated
by filtering.
• To separate the salt from the water, you must evaporate
the water. Solutions are TRANSPARENT (you can see
through them).
• 2) Tinctures: a solution where the solute is dissolved in
alcohol (ethanol). Some things which cannot dissolve in
water can dissolve in alcohol.
• This includes tincture of iodine, which is used to disinfect
cuts. It consists of iodine dissolved into alcohol.
• 3) Amalgam: a solid solution where a metal is dissolved into mercury (Hg).
Metals commonly used to make amalgams with mercury are silver (Ag) and
gold (Au), which were used for dental fillings until porcelain and composite
substances became more widely used for that purpose.
•
• 4) Alloys: metals can not chemically bond with each other, but they can be
mixed together to enhance their properties. Iron (Fe) is a strong metal that is
useful for making into structural shapes, but it does have drawbacks. It can
rust and it is quite soft. Mixing in carbon (C) makes an alloy known as steel.
This steel can be further enhanced by adding yet more metals, like chromium
(Cr), molybdenum (Mo) or cadmium (Cd).
• Gold is pretty to look at, but it is too soft on its own to fashion durable jewelry.
24 karat gold is pure gold, 14 karat gold is more than half pure gold, but silver
(Ag) and copper (Cu) are added to make the gold item more durable. 18 karat
white gold is an alloy of gold, palladium, nickel and zinc, or gold and platinum
or palladium.
•
• Heterogeneous (varying composition throughout the sample)
mixtures include:
•
• 1) Muddy water. The composition towards the bottom is mostly
mud, towards the top it’s mostly water. When shaken, the particles
will never be dispersed evenly enough to be considered
homogeneous.
•
• 2) Italian salad dressing: The different ingredients separate by
density with the oil on top and the vinegar and water at the bottom
with various pieces of chopped garlic and pepper at different levels
with varying concentration. As with muddy water, the particles are
too large to form a homogenous mixture.
•
•
• 3) Soil: this contains microscopic rock fragments, organic
debris and other items, depending on where you find it.
•
• 4) Cat vomit: this amazing material can contain a wide
assortment of components, including partially digested dry
or wet food, stomach juices, animal bones, fur and other
items which vary widely from cat to cat and from vomit to
vomit.
• These components are not mixed together regularly, upon
examination of the vomit pile, one might see more fur on
one side and more crunched-up dry food on the other.
•
Figure 1.01 Classification of matter
 Properties of Matter

• A set of unique characteristics that distinguishes one

substance from the other are called properties. There are two
categories of measurable properties of matter: Extensive and
Intensive properties.
•
• Extensive Properties: These are properties in which the
measured value is dependent on the amount or quantity of
substance present in the given sample e.g. mass and volume.
•
• Intensive Properties: These are properties in which the
measured value does not depend on the quantity of
substance present e.g. density , colour, taste.
•
•
 Physical Changes and Properties

• Physical Changes: Changes that change only the appearance of a substance, not its
chemical identity.
• Physical Properties: Properties that can be observed through physical change
•
• Physical
• Change Physical Property
•
• Melting Melting point (the temperature at which a substance turns from
a solid to a liquid)
•
• Boiling Boiling point (the temperature at which a substance turns from
a liquid to a gas)
•
• Dissolving Solubility (the amount of solute that can be dissolved in a solvent)
•
• Evaporating Vapor pressure (the pressure exerted by a vapor at vapor-liquid equilibrium)
•
• Crushing Malleability (the ability to be hammered or rolled into thin sheets)
•
• Stretching Ductility (the ability to be stretched into a wire)
•
• Specific heat (the heat it takes to raise the temperature of 1gram by 1 degree
Kelvin)
•
• Heat of Fusion (the heat it takes to melt 1 gram of solid at the melting point)
•
• Heat of Vaporization (the heat it takes to boil 1 gram of liquid at the boiling
point)
•
• Density (the mass of a substance per unit volume)
•
• Electrical & Heat Conductivity (the ability to pass heat or electricity
• through a substance)
 Chemical Properties and Changes

• Chemical Changes: Changes that result in changing the chemical composition of a substance.
Can be reversed only by another chemical change.
•
• Chemical Properties: Properties that can only be observed through chemical change.
•
• Chemical Change Chemical Property
• Corrosion of metals, flammability Reactivity (the likelihood of one substance to undergo
a chemical reaction with another substance)
• Chemical decomposition e.g.
hydrogen peroxide decomposes to Stability (the likelihood that a substance will not
form water and oxygen, but water decompose)
does not decompose spontaneously

• Combustion releases heat Heat of reaction (the energy absorbed or

• (exothermic) . Rarely do chemical released by a chemical reaction)
• Changes absorb heat (endothermic)
 States of Matter

• The atomic state of matter exists in three different phases:

solid, liquid and gas.
• Positive and negative charges attract each other. Attractive
forces between molecules are called intermolecular
attractive forces.
• The strength of these forces determines what phase of
matter a substance is in at a given temperature.
• Substances with weak attractive forces (London
dispersion) between their molecules tend to be gases at
room temperature, and substances with strong attractive
forces (ionic) tend to be solids at room temperature.
•
 States of matter contd.
• Phases of matter are simply stages of attraction.
• Gases are made of molecules with no attractive forces,
allowing the molecules to fly freely past each other.
• Liquids are made of molecules with stronger attractive
forces, allowing the molecules to flow past each other,
but still stay together.
• Solids are made of molecules or ions with strong
attractive forces, which lock the molecules into a
crystal lattice where the particles are free to vibrate,
but they cannot move relative to each other.
 PROPERTIES OF PHASES:
• SOLIDS:
– Molecules, atoms or ions are arranged into a regular,
geometric pattern called a crystal lattice.
– Molecules, atoms or ions vibrate in place. They do not
move relative to each other.
– Definite shape, definite volume.
• LIQUIDS:
– Molecules, atoms or ions can flow past each other.
– Because of intermolecular attractive forces, there is
resistance to flow, called viscosity.
– Viscosity increases as temperature decreases and
intermolecular attractive forces strength increases.
 Liquids contd.
– Liquid molecules near the surface can escape into the
vapor phase below the boiling point, a process called
evaporation.
– Shape of container (in absence of gravity, they form a
perfect sphere), definite volume.
• GASES:
– Gas molecules are extremely far apart compared
to the size of the molecules.
– Gas molecules travel in a straight line until they
collide with something.
 Gases contd.
– Collisions are elastic which means they don’t
lose any energy or speed.
– Gas molecules move faster when it’s hotter
(higher Kelvin temperature)
– The gas phase is the only phase that is affected
by changes in pressure.
– They spread out to take the shape and volume
of whatever container they are put into.
•
 Phase Change Diagram:
• Melting and boiling are endothermic
because energy has to be constantly added in
order for the change to be completed.
• Condensing and freezing are exothermic
because energy has to be constantly removed
in order for the change to be completed.
• Sublimation: attractive forces between
molecules are so weak that heating a solid
causes it to go directly into the gas phase.
• There are two common substances that
undergo this change;
– CO2 (s), also known as dry ice, and
– I2 (s).
Heating Curve showing phase change
• When a solid (A) is heated, its temperature increases until
the melting point is reached (B) (for H2O: 0oC or 273 K).
• The solid then absorbs potential energy as it melts (BC).
During the melting process, the temperature remains
constant until the entire solid has melted (C).
• Once the substance is completely in the liquid phase, the
temperature will increase as the liquid is continuously
heated (CD).
• Once the boiling point has been reached (D) (for H2O:
100oC or 373 K), the temperature will remain constant as
the substance turns from a liquid into a gas, a process
called boiling (or vaporization)(DE).
 Phase Equilibrium
• Once the substance is entirely in the gas phase (E), the
temperature will increase as heat is continually applied
(EF).
• The phase changes in this scenario are both
endothermic, because heat is being constantly applied.
• Phase Equilibrium: boiling and condensing both occur
at the boiling point (100oC for water),
• freezing and melting both occur at the melting point
(0oC for water).
• During the phase change, both phases exist at
equilibrium.
•
Modern Electronic Theory of Atom
• Electromagnetic Radiation
• Electromagnetic Spectrum
• Atomic Spectra........................................................
• Significance of Atomic Spectra................................
• The Quantum Theory..............................................
• The Wave Nature of the Electron
• Bohrs'Model of Atom..............................................
• Limitation of Boh'rs' Theory....................................
• The Uncertainty Principle........................................
• Quantum Number and atomic Orbital....................
• The Exclusion Principle............................................
• Hund.s rules of Maximum Multiplicity.....................
• Magnetic Properties of Atoms.................................
Modern Electronic Theory of Atom
• Electromagnetic Radiation:
• Proper understanding of the nature and propagation of
light forms the basis for proper elucidation of modern
electronic structure of an atom.
• Light is a radiant energy that produces a visual effect.
• In 1864, James Clerk Maxwell predicted that an
alternating current of high frequency in a circuit would
radiate energy in the form of waves - “electromagnetic
waves” - traveling into space with the speed of light
• Radiation is the energy traveling through space as a
series of waves.
• Electromagnetic radiation propagates in a vacuum
with the speed of light ‘c’ equal to 2.998 x 108 m/s.
• The electric field E and magnetic field H
components of the radiation are both orthogonal to
the direction of wave propagation and vary
sinusoidally with time.
 Wave parameters
• The wave parameters which can be used to
describe an electromagnetic radiation
completely are :
– Wavelength (λ) – defined as the distance between
two successive crests or troughs. It is measured in
meters, nanometers or angstrom units. 1 nm =
10-9 m, or 10-7 cm-1; 1 Å = 10-10 m
 – Frequency ( Ʋ) – defined as the number of waves
passing through a given point in a unit time.
– Wavenumber ( ) – defined as the number of
waves contained in one-centimeter length of
radiation
• The product of frequency and wavelength is a
constant – c: the speed of light.
λν=c
•
An Electromagnetic spectrum
 Quantization of Energy and the
Quantum Theory
• While studying the distribution of the wavelengths a nd the
intensities of light waves emitted by hot objects, such as hot
tungsten filament at different temperatures, Max Planck
(1900) assumed that :
– The atoms of a given solid must vibrate with respect to each other.
– The atoms can only vibrate with a certain frequency ( υ) or a
multiple (n) of it; = nυ
– The light that hot bodies emit must be composed of discrete
packets called quanta having the same frequency () as the vibrating
atoms that emitted them.
– The energy (E) of a quantum of light is proportional to the
frequency of the light
– i.e E = hυ where
– E = One quantum of energy,
• υ = frequency of the absorbed or emitted radiation,
• h = a constant called Planck’s constant. = 6.6252 x 10-34 Js
• E = hυ is the fundamental equation of the quantum
theory.
• Mathematical interpretations of the behaviour of
particles based on the quantum theory are called
quantum mechanics.
• It follows that the energy content of any system is not
continuously variable, but can be visualized as an
energy step-ladder;
• the low rung correspond to low energy levels, the high
rungs to high energy levels
 Energy step-ladder diagram

E4
•
• E3

• E2
• ΔE = E2 – E1 = hυ
• E1
• Energy absorbed or emitted by such a system
involves a transition of a component of the
system between two energy levels;
• Absorbed energy involves a transition to higher
energy level,
• emitted energy a transition to a lower energy
level.
• The amount of energy required for a quantum
jump from level E1 to level E2 is given by the
Planck’s equation
• E = hυ
• In an atom, when one of its components
system say electron is in E1 level, the atom is
said to be in its ground state ( state of low
energy);
• as it absorbs radiation it jumps to E2, (a state
of high energy) called excited state of an
atom.
 Photoelectric effect
• In 1905, Albert Einstein extended Planck’s
quantum theory to include all light (not just the
light emitted by hot bodies), through his
experiments with the photo electric effect –
• Photoelectric effect is the emission of electrons
from the surface of a metal when the metal is
irradiated by light.
• The kinetic energies of the photo electrons are
proportional to the frequency of the radiation,
with each metal requiring a characteristic
frequency before electrons are ejected at all.
Kinetic energy of emitted electrons
• Thus Kinetic energy of electron , ½ mv2 = hυ - hυo
• According to Einstein, the term ‘hυ’ corresponds to the
energy needed to remove an electron from the metal.
• If a light quantum does not have this energy
(corresponding to the minimum frequency (υo), then
no electrons whatever are emitted, as observed.
• If h > ho the electrons are emitted and the difference
(h - ho) is the energy that is left over and can be used
for the kinetic of the electron.
• Thus the equation ½ mv2 = hυ - hυo predicts that
a simple linear relation should exist between the
energy of the liberated electron and the
frequency of the light.
• As the frequency of the light is increased, h
increases and the energy of the photoelectron
should increase.
• h, a constant in the slope of the line relating the
energy of the photoelectron and should be the
same for all metallic surfaces.
•
• The wave theory of light predicted a dependence of photo
electrons energies on the intensity of the light beam.
• According to Einstein postulate; The interaction of a photon with
an electron of the metal caused the photoelectric effect.
• In a collision, the photon vanishes and all the energy is given to the
electron.
• In order to dislodge the electron, the photon has to have a certain
minimum energy (given by its frequency), and any excess energy
over that needed to disengage the electron is imparted to the
electron as kinetic energy.
• Thus increasing the intensity of light of a given frequency increases
the number of photons but does not increase the energies of the
photons.
• Hence when the intensity of the light is increased, more electrons
are ejected, but the energies of these electrons are not altered.
• While the wave character of radiation is
verified by experiments involving diffraction
and interference phenomena,
• The particle character of radiation in verified
by experiments involving energy exchanges
between radiation and matter.
 Atomic spectra
• When a beam of parallel rays of white light
(made of different wavelengths) enters the
face of a triangular glass prism, all of the
different colour rays comprising white light are
bent, but some are bent more than others.
• The result is that the light emerging from the
prism is “split” into a variety of different
colours.
• This process is called dispersion of light. The
dispersion of light forms the basis of
spectroscope.
 Light dispersion
•
• When white light (sun rays) or light emitted by hot
objects is passed through a glass prism, the result
is that the light emerging from the prism is split
into a variety of different colours, i.e a continuous
spectrum
• Continuous spectrum consists of light of all
wavelengths.

•
• When the light emitted from a source is
analyzed, the spectrum obtained is called an
emission spectrum.
• On the other hand, the spectrum obtained
after light from some source has passed
through a substance is known as an
absorption spectrum.
• To study the spectra of atoms, the element under consideration is
heated or subjected to electrical discharge.
• The sample which has been thus excited is used as a source and the
light passed through a prism.
• The pattern emerging from the prism is atomic spectrum of the
element used as source .
• Atomic spectra have definite sharp lines and many dark spaces.
• Atomic spectra thus consist of a few characteristic wavelengths
(corresponding to the sharp lines) rather than a continuous series
of wavelengths.
• The lines spans from the ultraviolet through visible to the infrared
region.
•
 Line spectra
•
•
• The study of the spectra of elements is an important source of information in the determination of
the structure of atoms.
• From the geometry of the system, the wavelength of the light associated with each line in the
atomic spectrum could be determined by use of an equation called Rydberg equation:
•
1 1 1
• = 𝑅𝐻 −
𝜆 𝑛12 𝑛22
•
• where λ is the wavelength of the light corresponding to a given line in the spectrum,
• R is a constant called Rydberg constant = 109678 cm-1
• n1 is a dimension less integer and
• n2 is another dimension less integer greater than n1.
• Thus when n1 = 1, n2 may be any integer greater than 1 and each value of n2 yields a wavelength ,
corresponding to a line in the spectrum of atom under consideration.
•
• Lines in the ultraviolet region of the atomic spectrum
of hydrogen were first observed by a scientist by name
Lyman,
• while the ones in the visible region were observed by
Johan Balmer.
• In the infrared regions, 3 sets of lines were observed:
at near infrared by Paschen, far infrared by Brackett
and Pfund.
• These lines are respectively referred to as Lyman,
Balmer, Paschen, Brackett and Pfund series after their
discoverers.
• Rydberg equation can be used for each line.
• Series n-value m-values
• Lyman (1916) 1 2,3,4-
Balmer(1885) 2 3,4,5...
Paschen 3 4,5,6...
(1908)
Brackett(1922) 4 5,6,7...
Pfund(1924) 5 6,7 ...
The allowed energy levels in the hydrogen atom and
the various transitions giving rise to series of lines
 Bohr Model of Hydrogen atom

• In 1913, Niels Bohr proposed a theory for the

electronic structure of the hydrogen atom that
explained the line spectrum of this element.
• The significance of the line spectrum of hydrogen is
that only certain energies are allowed for the electron
in the hydrogen atom.
• Thus energy is emitted or absorbed by an atom when
an electron jumps from one energy level to the other.
• The energy of such a system is said to be quantized.
• The following are the postulates of Bohr’s theory
 Bohr’s postulate 1
• The electron of the hydrogen atom can exist only
in certain spherical orbits (which are also called
energy levels or shell).
– These shells are arranged concentrically around the
nucleus.
– Each shell is designated by a letter K, L, M, N, O,…or
by n = 1, 2, 3, 4, 5, 6,.
 Postulate 2
• The electrons has a definite energy characteristic
of the orbit in which it is moving.
– These orbits are called energy levels.
𝑚𝑒 4
𝐸𝑛 = −
8 ∈2 ℎ2 𝑛2
– m= mass of electron
– e= electronic charge
– ∈ = 𝑝𝑒𝑟𝑚𝑖𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑓𝑟𝑒𝑒 𝑠𝑝𝑎𝑐𝑒
– h= Planck’s constant
– n= positive integer : 1, 2, 3, etc.
 Postulate 3
• The electron cannot take all possible orbits. It can
move only in those orbits in which the angular
momentum of the electron (mvr) is a whole number
multiple of h/2π.
– This is known as the principle of quantization of angular
momentum
– i.e mvr = nh/2π
– where m = mass of the electron,
– v = velocity of the electron in its orbit,
– r = distance between the electron and the nucleus,
– n = a positive integer,
– h =Planck’s constant
 Postulate 4
• When the electron moves in the same orbit
it does not change its energy and the orbit
is said to be stationary.
 Postulate 5
• When an electron moves from one orbit to the
other it either emits or absorbs energy.
– It emits energy when it drops from an orbit of higher
energy (E2) to one of lower energy (E1).
– But it absorbs energy when moving from low energy
level E1 to high energy level E2.
– Both these processes obey Planck’s equation ΔE = hυ
 Postulate 6
• When an electron is in a stationary orbit, two
types of forces which are in operation
– Viz (i) electrostatic force of attraction between
the electron and the nucleus (which tends to Pull
the electron towards the nucleus) and
– (ii) Centrifugal force due to the motion of the
electron (which tends to throw the electron out
of its orbit) must balance each other.
 Success of Bohr’s theory
• The most remarkable success of Bohr’s theory was in
explaining the spectrum of hydrogen and hydrogen-like
atoms.
• On the basis of Bohr’s theory the following successful
calculations were made Viz
– (i) The radius (r) of the allowed orbit in hydrogen atom
– (ii) The energy of the electron in the allowed orbit (En).
– (iii) The frequency ( ), wavelength () and wave number ( )
of the spectral lines of hydrogen atom.
– (iv) The Bohr theory could be used to derive the Rydberg
formula
– i.e the value of the Rydberg constant RH for hydrogen
atom could be calculated
Calculation of the radius (r) of the permissible orbit in
the atom of Hydrogen.

• Hydrogen atom consist of a central, rather massive positive

nucleus with one electron revolving about it in an orbit of
radius r.
• Let v = the velocity and m = the mass of the revolving
electron;
• Then from the principle of quantization of angular
momentum (Postulate 3)
•
𝑛ℎ
• 𝑚𝑣𝑟 = 1
2𝜋
•
𝑛ℎ
• ∴ 𝑣= 2
2𝜋𝑚𝑟
• The force holding the electron in a circular
orbit is supplied by the coulombic
(electrostatic) force of attraction between the
positively charged nucleus and the negatively
charged electron:
𝑒2
• 𝐹= 3
4𝜋∈𝑜𝑟 2
– Where ∈o is the permittivity of free space
= 8.85419 x 10-12 C2/Nm2
• The coulombic attractive force is balanced by
the centrifugal force
𝑚𝑣 2
𝐹= 4
𝑟
• Equating equation 3 and 4 and making v2 the
subject formula:
𝑒2 𝑚𝑣 2
• = 5
4𝜋∈𝑜𝑟 2 𝑟
𝑒2
• 𝑣2 = 6
4𝜋∈𝑜𝑚𝑟
𝑛ℎ
• But from equation 2, 𝑣 =
2𝜋𝑚𝑟
𝑛2 ℎ 2
Impyling that 𝑣2 = 7
4𝜋2 𝑚2 𝑟 2
Equating 6 and 7:
𝑒2 𝑛2 ℎ 2
• 𝑣2 = =
4𝜋∈𝑜𝑚𝑟 4𝜋2 𝑚2 𝑟 2
• making r the subject formula
∈𝑜 𝑛 2 ℎ 2
• 𝑟= 8
𝜋𝑚𝑒 2
∈𝑜 ℎ 2
• Let ao = then equation 8 becomes
𝜋𝑚𝑒 2
• r = n2ao 9
Substituting the values of the constants:
ao = 0.5290 Å , and r = 0.5290 n2
 Calculation of the energy of the
electron in the allowed orbit
• The total energy of the electron in an atom is equal to the sum of its kinetic energy
and potential energy
• ETotal = KE + P.E 11
• The kinetic energy (due to the motion of the electron) = mv2/2
• while the potential energy of an electron and a proton separated by a distance r is
given by coulombs law:
• When two opposite charges attract each other, the P. E by convention is negative:
𝑒2
• P.E. =
4𝜋∈𝑜𝑟
𝑒2
• ∴ Etotal = 1/
2 mv
2 - 12
4𝜋∈𝑜𝑟

𝑒2 𝑚𝑣 2
• Recall from equation 5, =
4𝜋∈𝑜𝑟 2 𝑟
•
𝑒2
• mv2 = 4𝜋∈𝑜𝑟
13

• Substitute 13 In 12
 𝑒2 𝑒2
• E = -
8𝜋∈𝑜𝑟 4𝜋∈𝑜𝑟
• Factorizing
𝑒2
• ET = - 14
8𝜋∈𝑜𝑟
∈𝑜 𝑛 2 ℎ 2
• From equation 9, 𝑟 =
𝜋𝑚𝑒 2
• Substituting for r in equation 14
𝑒2 𝜋𝑚𝑒 2 𝑚𝑒 4
• ET = - x =−
8𝜋∈𝑜 ∈𝑜 ℎ 2 𝑛 2 8∈𝑜2 ℎ2 𝑛2
𝑚𝑒 4
• En = − 15
8∈𝑜2 ℎ2 𝑛2
• En is the energy of the nth – orbit
• m= mass of the electron = 9.11 x 10-31 kg
• e= electronic charge = 1.602 x 10-19 C
• ∈ 𝑜 = 8.85419 𝑥 10 − 12 𝐶2𝑁/𝑚2
• h= Planck’s constant = 6.626 x 10-34J.s
• Substituting the constants into equation 15,
2.179 𝑥 10−19
• En = - 2 J
𝑛
•
13.6
• or − - eV
𝑛2
• The lowest energy state obtained by putting n
= 1 is called the ground state.
• The next higher state obtained by putting n =
2 is called the excited state.
• The ground state of an atom refers to the state
of low energy, while the excited state is the
state of high energy
 Calculation of the frequency, wavelength, and
wave number

• According to Bohr’s theory, the observed

spectrum of the hydrogen atom is due to
transitions from one allowed energy state to
another.
• When an electron jumps from an energy level
n2 of an energy E2 to level n1 of an energy E1,
the energy change is given as ΔE= E2-E1.
• Thus applying equation 15 where
•
 𝑚𝑒 4
• En = −
8∈𝑜2 ℎ2 𝑛2

𝑚𝑒 4 𝑚𝑒 4
• E1 = − and E2 = −
8∈𝑜2 ℎ2 𝑛12 8∈𝑜2 ℎ2 𝑛22

𝑚𝑒 4 𝑚𝑒 4
• ΔE= E2-E1 = − - (− )
8∈𝑜2 ℎ2 𝑛22 8∈𝑜2 ℎ2 𝑛12

𝑚𝑒 4 𝑚𝑒 4 𝑚𝑒 4 1 1
ΔE = − = − 16
8∈𝑜2 ℎ2 𝑛12 8∈𝑜2 ℎ2 𝑛22 8∈𝑜2 ℎ2 𝑛12 𝑛22
• This energy change obeys Planck’s law
𝑚𝑒 4 1 1
• ΔE = hυ = −
8∈𝑜2 ℎ2 𝑛12 𝑛22

𝑚𝑒 4 1 1
• Ʋ= − 17
8∈𝑜2 ℎ3 𝑛12 𝑛22
• Where Ʋ is the frequency of the line in the
hydrogen spectrum.
• But λν=c
𝑐
Ʋ=
𝜆
 𝑐 𝑚𝑒 4 1 1
• 𝜈= = −
𝜆 8∈𝑜2 ℎ3 𝑛12 𝑛22

𝑐 𝑚𝑒 4 1 1
• = −
𝜆 8∈𝑜2 ℎ3 𝑛12 𝑛22

1 𝑚𝑒 4 1 1 1 1
• = − = RH 2 −
𝜆 8∈𝑜2 ℎ3 𝑐 𝑛12 𝑛22 𝑛1 𝑛22

𝑚𝑒 4
• Where RH =
8∈𝑜2 ℎ3 𝑐
 Limitations of Bohr’s theory

• (i) Bohr theory had explained the existence of various lines in

Hydrogen spectrum but could not account for the
intensities/brightness of the spectral lines.
• (ii ) Bohr’s theory successfully explained the observed spectrum of
Hydrogen atom (1 electron), helium ions He+, (1 electron), Lithium
ions Li2+ (1 electron Be3+ (1 electron), but failed to account for the
spectra of many electron systems (i.e atoms containing more than
one electron).
• (iii) There was no satisfactory justification for the quantization of
angular momentum.
• (iv) Bohr’s Theory could not explain why atoms should combine to
form in chemical bond.
• (v) Bohr predicted the position and speed of an electron with
certainty.
 Wave Description of an Electron:

• Owing to the inability of Bohr model to explain

successfully certain phenomena
– like Zeeman effect or stark effect and
– the structure of many electron system,
a new model called wave (quantum) mechanical model of
the atom was developed and championed by three
scientists viz.
• Louis de Broglie,
• Werner Heisenberg and
• Erwin Schrodinger
 de Broglie Hypothesis:

• Louis de Broglie postulated that the electron

behave both as a material particle and as a
wave.
• Many experiments carried out have shown
that light appears wave-like in some instances
and particle-like in others.
• This ability of light or matter in general to
exhibit both wave and particle behaviour is
referred to as wave particle duality.
 Experimental proof of light duality:

• Light as a wave:
– (i) The dispersion of white light into its spectrum
by a prism.
– (ii) The diffraction and interference experiments of
electromagnetic radiation.
• Light as a particle:
– (i) Photoelectric effect
– (ii) Oil drop experiment
• Niels Bohr in proposing his theory considered
electron as a material particle revolving round
the nucleus in spherical orbits.
• Now since electromagnetic wave could exhibit
particle like behaviour,
• In 1924, Louis de Broglie argued that a micro-
particle like electron when in motion will be
associated with a wave character.
• He visualized the electron wave behaviour as a
standing wave extending round the nucleus in a
circular orbit.(Fig.2.7).
• Broglie put his idea into a quantitative scheme by
de

examining two fundamental energy equations

• Einstein equation E =mc2 2.5.1
• Planck’s equation E = hƲ 2.5.2
• According to de Broglie, the two characteristic
energies should be equivalent to each other. Thus
equating 2.5.1 and 2.5.2.
•
• E = mc2 = hƲ
ℎ𝑐
𝑚𝑐2 =
𝜆
ℎ
• mc =
𝜆
•
 ℎ
• 𝜆=
𝑚𝑐
ℎ
• 𝜆= 2.5.3
𝑝

Where p = momentum of the particle = mv. . Equation

2.5.3 I s called de Broglie equation.
This equation predicts that a particle of mass m
moving with velocity ,v will have a de Broglie
wavelength given by

ℎ
𝜆=
𝑝
 The Bohr atom in the light of wave
mechanical model.
• Bohr in proposing his model made some non-
classical assumptions such as
• - The existence of stationary electron orbits
• - The quantization of angular momentum of an
electron.
• - Definite amount energy characteristic of the
orbit in which electron is revolving.
• In the light of quantum mechanical model, the
electron possess wave properties.
• The behaviour of the electron while in motion is
that of a standing wave which extends around the
nucleus in a circular orbit.
• For the wave pattern around the orbit to be
stable and be in phase,
• this wave must fit exactly around the
circumference of the circular obit
• i.e an integral multiple of the wavelengths must
equal the circumference of the orbit.
• Mathematically;
• nλ = 2πr 2.5.4
• From deBroglie’s equation(equation 2.5.3) ,
ℎ
𝜆=
𝑚𝑣
• Comparing the values of λ:

2𝜋𝑟 ℎ
• 𝜆= =
𝑛 𝑚𝑣
𝑛ℎ
• 2𝜋𝑟 =
𝑚𝑣
ℎ
• mvr =n 2.5.5
2𝜋
• Where n = 1, 2, 3...
• Thus the principle of quantization of angular
momentum of an electron as assumed by Niels Bohr
has been proven to be correct by wave mechanical
model of an electron.
 Heisenberg Uncertainty Principles.

• According to Bohr’s theory, the position of an

electron as well as its speed in a given Bohr
orbit could be precisely determined.
∈𝑜 𝑛 2 ℎ 2 𝑛ℎ 𝑒2
• 𝑟= 2 , 𝑣= =
𝜋𝑚𝑒 2𝜋𝑚𝑟 2∈𝑜ℎ𝑛
• Accordingly there is a fixed amount of energy
for any given stationary orbit.
• Energy changes only when there is transition
from one orbit (energy level) to the other.
• A pertinent question to ask is what happens
when the electron is on its way to the next
orbit?
• Put differently is it possible to describe exactly
the path of an electron?
• In an attempt to answer these questions, Werner
Heisenberg in 1927 discovered that the position
and the momentum of a micro particle cannot be
accurately specified at the same time.
• Heisenberg showed that if the position of an
electron to be measured is within a distance Δx,
• Then a photon of light with wavelength, λ
approximately equal must be used When the
photon is made to interact with electron.
•
• During this interaction or collision there will
be a transfer of momentum to the electron
resulting in a change in the electron’s position.
• Locating the electron’s position requires
knowing how much momentum P (mv) is
transferred to the electron.
ℎ
• From deBroglie equation, 𝜆 =
𝑚𝑣
• the higher the wavelength the smaller the
momentum and the smaller the wavelength
the greater the momentum.
• Thus to determine how much momentum is
transferred, a photon of smaller wavelength is
required.
• But the momentum of the photon will be very
high if the wavelength is very small, and
• Consequently the position of the electron will
change due to the large momentum of the
photon striking it.
• This difficulty which has been expressed
mathematically in equation 2.5.6 is called the
uncertainty principle.
ℎ
• Δx.ΔP = 2.5.6
4𝜋
• Δx = uncertainty in the particles position.,
• ΔP = uncertainty in the momentum of the
particle,
• h = Planck’s constant.
• Thus according to this principle, there is
always uncertainties in trying to determine
both the position and momentum of a micro-
particle simultaneously.
• The more knowledge we have concerning the
particle’s position, the more uncertain will be
the value of its momentum and vice versa.
 Schrodinger wave equation

• Louis de Broglie described the wave nature of an

electron in motion as that of a standing wave
extending round the nucleus and has shown that
ℎ
the wavelength is given as : 𝜆 =
𝑚𝑣
• A standing wave is a wave whose nodes do not
move as it is the case in a vibrating string.
• According to Heisenberg Uncertainty Principle,
the description of the exact path of an electron
as it moves around the nucleus is impossible.
• Based on this, Erwin Schrodinger in 1926,
proposed a mathematical model to describe
electrons wave behaviour in an atom and
energies of the electrons:
• Every system at the subatomic level is associated
with a property called a wave function..
• If we consider a case of an electron confined to a
one-dimensional box of length L as shown in
Figure 2.8,
• the wave function is given as
2𝜋𝑥
• 𝜓= 𝐴𝑠𝑖𝑛 2.5.7
𝜆
• Comparing with the general classical wave equation:
2𝜋𝑥
• 𝑦= 𝐴𝑠𝑖𝑛
𝜆

𝜓 becomes the amplitude of the wave.

For the standing wave pattern to be stable, the
wavelength of the wave must be integrally related to
the distance L
nλ =2L 2.5. 8
Where n =1, 2, 3...
Combining equations 2.5.7 and 2.58, we have that
2𝜋𝑥 2𝐿
𝜓= 𝐴𝑠𝑖𝑛 , 𝜆=
𝜆 𝑛
•
 2𝜋𝑥
• 𝜓 = 𝐴𝑠𝑖𝑛 2𝐿
𝑛
2𝜋𝑥
• 𝜓 = 𝐴𝑠𝑖𝑛 2.5.9
𝐿
• Equation 2.5.9 represents wave function for possible standing
waves.

  2

  2

  2
• The total energy of the electron in the box is
given as
• ETotal = Kinetic energy + Potential Energy
•
• E = K.E + P.E
• KE = 1/2 mv2
ℎ
• But 𝑚𝑣 = (de Broglie equation)
𝜆
ℎ ℎ2
• 𝑣= ; 𝑣2 =
𝑚𝜆 2𝑚2𝜆2
𝑚𝑣2 𝑚ℎ2
• 𝐾. 𝐸 = =
2 2𝜆2𝑚2

ℎ2
• K.E = 2.5.10
2𝜆2𝑚
 𝑒2
• Recall that P.E = -
4𝜋𝜖𝑜𝑟
• ET = K.E + P.E

ℎ2 𝑒2
• ET = 2 - 2.5.11
2𝜆 𝑚 4𝜋𝜖𝑜𝑟
𝑒2 ℎ2
• E + =
4𝜋𝜖𝑜𝑟 2𝜆2𝑚
 2𝑚
• Multiply through by
ℎ2
2𝑚𝐸 2𝑚 1
• + V= 2
ℎ2 ℎ2 𝜆
𝑒2
• Where V =
4𝜋𝜖𝑜𝑟
2𝑚 1
• 𝐸+𝑉 = 2 2.5.12
ℎ2 𝜆
2𝐿
• But 𝜆 = (2.5.8)
2
𝑛
4𝐿
• 2
𝜆 = 2
𝑛
• Substituting for λ2 in equation 2.5.12
 2𝑚 𝑛2
• 𝐸+𝑉 =
ℎ2 4𝐿2
𝑛2ℎ2
• E+V= 2.5.13
8𝑚𝐿2
• But E is the total energy = KE + PE, substituting
for E in equation 2.5.13
𝑛2ℎ2
• KE + PE + V =
8𝑚𝐿2
𝑒2 𝑒2
• Recall that PE = - and V=
4𝜋𝜖𝑜𝑟 4𝜋𝜖𝑜𝑟
𝑒2 𝑒2 𝑛2ℎ2
KE - + =
4𝜋𝜖𝑜𝑟 4𝜋𝜖𝑜𝑟 8𝑚𝐿2
𝑛2ℎ2
KE = 2 2.5.14
8𝑚𝐿
• Thus equation 2.5.14 gives the kinetic energy of the
electron in the box and it depends strongly on the
value of n.
• Equation 2.5.14 further reveals that the potential
energy is zero for a particle that is confined within a
one-dimensional box.
ℎ
• But from de Broglie equation: 𝜆 =
𝑚𝑣
• A partial differential equation which describes the
wave motion of a particle confined within a one-
dimensional space as depicted in Figure 2.8 is given as
 𝜕2𝜓 𝜔2𝜓(𝑥)
• + =0 2.5.15
𝜕𝑥2 𝑣2
• Where 𝜔 𝑡ℎ𝑒 𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 = 2𝜋𝜐,
• v = λυ
• Substituting for v and 𝜔 in equation 2.5.15
𝜕2𝜓 4𝜋2𝜐2𝜓(𝑥)
• + = 0
𝜕𝑥2 2 2
𝜐𝜆
4𝜋2 𝜕2𝜓
• 𝜓 =− 2
𝜆 𝜕𝑥
 𝜆2 𝜕2𝜓
• 𝜓 𝑥 =− 2 2 2.5.16
4𝜋 𝜕𝑥
ℎ
• But 𝜆 = (𝑑𝑒 𝐵𝑟𝑜𝑙𝑖𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛)
𝑚𝑣
2
ℎ
• 𝜆2 = 2 2
𝑚𝑣
• Substituting for λ2 in equation 2.5.16
ℎ2 𝜕2𝜓
• 𝜓 𝑥 = − 2 2 2 2 2.5.17
4𝑚 𝑣 𝜋 𝜕𝑥
• Multiplying both sides of equation 2.5.17 by
2mv2

ℎ2 𝜕2𝜓
• 2mv2𝜓 𝑥 = −
2𝑚𝜋2 𝜕𝑥2
 4𝑚𝑣2
• 2mv2 =
2
4𝑚𝑣2 ℎ2 𝜕2𝜓
• 𝜓 𝑥 = −
2 2𝑚𝜋2 𝜕𝑥2
𝑚𝑣2 = E
•
2

ℎ2 𝜕2𝜓
• 4𝐸𝜓 𝑥 = −
2𝑚𝜋2 𝜕𝑥2

ℎ2 𝜕2𝜓
• 𝐸𝜓 𝑥 = − 2.5.18
8𝑚𝜋2 𝜕𝑥2
• Equation 2.5.18 is the Schrodinger formulation
which gives the kinetic energy of the system.
• The total energy of the particle is
• ET = KE + P.E
ℎ2 𝜕2𝜓
• 𝐸= − +V
8𝑚𝜋2 𝜕𝑥2
• Multiply through by 𝜓
ℎ2 𝜕2𝜓
• 𝐸𝜓 𝑥 = − + V𝜓
8𝑚𝜋2 𝜕𝑥2
 ℎ2 𝜕2𝜓
• 𝐸𝜓 − 𝑉𝜓 = −
8𝑚𝜋2 𝜕𝑥2

ℎ2 𝜕2𝜓
• 𝐸−𝑉 𝜓+ =0 2.5.19
8𝑚𝜋2 𝜕𝑥2
• Equation 2.5.19 is called Schrodinger one-
dimensional wave equation.
• For an electron in an atom which is confined in a
three dimensional space, with x, y, z coordinates,
equation 2.5. 19 becomes:
 ℎ2 𝜕2𝜓 𝜕2𝜓 𝜕2𝜓
• 2( + 2 + 2) + (E-V)𝜓 = 0 2.5.20
8𝑚𝜋 𝜕𝑥2 𝜕𝑦 𝜕𝑧

𝜕2𝜓 𝜕2𝜓 𝜕2𝜓

• If we set ( 2 + 2 + 2) = 𝛻2
𝜕𝑥 𝜕𝑦 𝜕𝑧

• Then equation 2.5.20 becomes

ℎ2
• 𝛻2𝜓 + (E-V)𝜓 = 0 2.5.21
8𝑚𝜋2

• Where ∇2 (pronounce del-square) is known

as Laplacian operator .
• Equation 2.5.21 represent the Schrodinger
wave equation for the electrons in the atom.
The essential features of this equation
• a) The first term gives the kinetic energy of the
electron
• b)The second term gives
– The total energy (E) of the electron in the atom or
molecule
– The potential energy V, which consists of:
attractive potential of the nucleus for the electron
electron - electron repulsions with other
electrons., attractions to electrons in any other
nuclei in a molecule
• (c) Being a time independent second order
differential equation, it has an infinite number of
solutions for the wave function (𝜓).
• (d) The acceptable solution for the wave function
must satisfy the following conditions.
• (i) The solution must be single value. Implying that at
any given point in space defined by a set of
coordinates x1 , y, z, the amplitude should have only
one value.
• (ii)The first derivative of the wave function that is,
𝜕𝜓 𝜕𝜓 𝜕𝜓
• , , should be continuous.
𝜕𝑥 𝜕𝑦 𝜕𝑧
 • The wave function it self must be finite and continuous as well.
• (iii) If 𝜓 represents a bound state then it must varnish at
infinity
∞ 2
• i.e 0
𝜓 dr = 0
• Wave functions which satisfy the above conditions are said
to be well-behaved wave functions and are called Eigen -
functions.
• The vales of E which correspond to these eigen-functions
are called the Eigen - values.
• A wave function that is a solution of the Schrodinger wave
equation, that is the eigen-function for an electron is called
an atomic orbital.
•
 The physical significance of wave function :
Max Born interpretation.

• We know that the wave function represents

the amplitude of the electron wave.
• According to the electromagnetic wave
theory, the square of the amplitude is a
measure of the intensity of light.
• In the case of an electron, the intensity refers
to the electron charge density, and
Schrodinger’s interpretation reveals that:
 ∗
• eψ 𝑥 𝜓 𝑥 is charge density while
∗
• eψ 𝑥 𝜓 𝑥 𝑑𝑥 is the magnitude of the charge between x
and x + dx.
• This interpretation was faulted by Max Born who
considered the square of the wave function asa probability
density.
∗
• According to Max Born ψ 𝑥 𝜓 𝑥 𝑑𝑥 represents the
probability of locating an electron between x and x + dx.
• Thus the physical significance of the wave function is that
the probability of finding an electron in any given region is
proportional to the square of the wave function
• Mathematically, this is expressed as
∗
• Probability density ∝ /𝜓𝜓 /
– Where 𝜓 * is the complex conjugate of 𝜓.
• The higher the value of 𝜓 2 the greater the probability
of locating the electron and vice versa.
• Thus the total probability of finding the electron in any
volume element is unity
• i.e 𝜓 𝑥 𝜓 𝑥 𝑑𝑥 = 1

• Where the integration is over all space accessible to

the electron.
•
 Atomic orbitals and quantum numbers:

• The wave functions which are solutions to the Schrodinger equation

- the eigen - functions for an electron are called Atomic orbitals .
• Since the square of this wave function is proportional to the
probability of the presence of an electron,
– an orbital is therefore the space around the nucleus with the highest
probability of locating an electron.
• If a boundary is drawn enclosing this region of high probability the
configuration and size of the figure obtained gives the shape and
size of the atomic orbital.
• The shape of an orbital can therefore be defined as the surface of
constant probability density, which encloses some large fraction
(about 95%) of the probability of locating an electron..
• The wave function is usually written as
• 𝜓 = 𝜓(x,y,z)
– where x,y,z are the Cartesian coordinates of a
point.
• The best way of expressing this wave function
is in terms of spherical polar coordinate as
shown in Figure 2.9
•
 

• Fig 2.9 Spherical polar coordinates which describes the position of

a point P in three-dimensional space.
•
• Figure 2.9 depicts 𝜓 as a function of three
coordinates ( r, θ, φ) and their quantum
numbers (n, l, m).
• Thus the wave function can be written as
• Ψn,l,ml (r, θ, φ)
• where n = principal quantum number,
– l = azimuthal or orbital angular quantum number,
– ml = magnetic quantum number,
– r = the radial distance from the nucleus,
– θ = the angular distance from the polar axis,
– φ = the angular distance from the reference
vertical plane
• Thus the wave function is a product of two
functions viz:
– radial wave function and
– angular wave function:
• 𝜓 = 𝑅𝑛, 𝑙 𝑟 . 𝑌𝑙 , 𝑚𝑙 (Θ, 𝜙) 2.6.1
• The radial part of the wave function 𝑅𝑛, 𝑙 𝑟
– shows how the probability of locating an electron
varies with distance r, from the nucleus and
– it contains the principal quantum number n and
– l, the orbital angular quantum number.
• The angular wave function 𝑌𝑙, 𝑚𝑙(Θ, 𝜙),
– shows how the probability varies with direction
and contains two quantum numbers l and ml..
 Quantum numbers

• Quantum numbers are numbers which labels the

quantized state of an electron thereby specifying its
properties.
• These numbers serves as an identification numbers for
an individual electron in the atom. They are:
• (1) Principal quantum number - n
• (ii) Azimuthal or orbital angular momentum quantum
number: 𝒍
• (iii) Magnetic quantum number - 𝑚𝑙
• (iv) Spin quantum number - ms
Significance of quantum numbers
 Significance of quantum numbers
• The principal quantum number:
• This quantum number denoted by n occurs only in the radial part
[Rn , l (r)] of the wave functions obtained by solving the
Schrodinger’s equation.
• It determines the size of the orbital as well as the energy of the
electron .
• The energy of an electron is given as:
𝑚𝑒 4
• En = −
8∈𝑜2 ℎ2 𝑛2
•
•
2.179 𝑧 10−18
• = - 𝐽
𝑛2
• This energy depends only upon the principal quantum number n
and
• n can be take any positive integral value ranging from 1 to ∞
• (i.e, n = 1, 2, 3, 4,.. ∞).
 Azimuthal or orbital angular
momentum quantum number:
• This quantum number denoted by 𝑙 determines the
shape of the orbital.
• It can take any integral value from zero up to a
number less than the principal quantum number
(i.e. l = 0,1,2..n-1).
• The value of 𝑙, the azimuthal quantum number is
customarily denoted by a letter.
– Electrons for which 𝑙 = 0 are termed s-electrons,
– for 𝑙 = 1, p-electrons,
– for 𝑙 = 2, d-electrons and for
– 𝑙 =3, f-electrons etc.
 𝑙 0 1 2 3 4
letter s p d f g
designation
• Correlating the orbital quantum number 𝑙 with
the principal quantum number (n) we have:
•
• n 𝑙 orbital designation
• 1 0 1s
• 2 0, 1 2s, 2p
• 3 0, 1, 2 3s, 3p, 3d
• 4 0, 1, 2, 3 4s, 4p, 4d, 4f
•
 Magnetic quantum number
• This quantum number denoted as 𝑚𝑙 determines
the orientation of the orbital of a given shape.
• For any given orbital, there are 2𝑙 + 1 possible
orientation which also gives the total number of
orbitals with the given value of 𝑙.
• Thus for 𝑙 = 0, 1, 2 ,3, the possible orientations
and hence the number of orbitals will be 1, 3, 5, 7
respectively.
• 𝑚𝑙 can take up any integral value (positive or
negative) ranging from -𝑙 to + 𝑙
• i.e 𝑚𝑙 = ±1. ±2, ±3 … .
• for: 𝑙 = 0, 𝑚𝑙 = 0
• 𝑙 = 1, 𝑚𝑙 = +1, 0, -1
• 𝑙 =2, 𝑚𝑙 = +2, +1, 0, -1, -2.

• The relationship existing between the values

of n, l and 𝑚𝑙 and the number of orbital is
given in Table 2.6.
Table 2.6.1 Relationship between the
n, 𝑙 𝑎𝑛𝑑 𝑚𝑙
Principal quantum Azimuthal quantum Magnetic quantum number Number of orbital Type of
number number orbital

N l ml (2l + 1) = n2
1 0 0 1 1s
2 0 0 1 2s
1 +1,0,-1 3 2p
3 0 0 1 3s
1 +1, 0, -1 3 3p
2 +2, +1, 0, -1,-2 5 3d

4 0 0 1 4s
1 +1,0,-1 3 4p

2 +2,+1,0,-1,-2 5 4d

+3,+2,+1,0,-1,-2,-3
3 7 4f
 Spin quantum number (ms)
• When electron occupies a given orbital with a
set of n, 𝑙 𝑎𝑛𝑑 𝑚𝑙 values, it does so with its
spin either up or down depending on the value
of the spin angular momentum of the electron.
• The spin momentum of an electron can have
a value of either +1/2 or -1/2 depending on
the two possible directions of rotation of the
electron.
 Shapes of Atomic orbitals:
• The general form of the solution of the Schrodinger
wave equation is expressed as:
• 𝜓 = 𝑅𝑛, 𝑙 𝑟 . 𝑌𝑙, 𝑚𝑙(Θ, 𝜙)
•
• This form of the solution consists of two parts viz:
– (i) 𝑅𝑛, 𝑙 𝑟 = the radial part of the wave
– (ii) 𝑌𝑙, 𝑚𝑙(Θ, 𝜙) = the angular part of the wave function.

The two parts are customarily considered separately.

 Radial part of the wave function:
• The radial wave function R depends on two
quantum numbers n and l,
• it determines the relative size of an orbital as
well as the variation of the orbital with
distance r, from the nucleus.
• Thus [𝑅𝑛, 𝑙 𝑟 ]2 gives the probability of finding
the electron at a distance r.
• Assuming, the electron is in a spherical shell
of volume V
4𝜋𝑟3
• Volume (V) =
3
• differentiating with respect to r
•
•
•
 𝑑𝑉 4𝜋𝑟2
• =3 = 4𝜋𝑟2
𝑑𝑟 3
• dV = 4𝜋𝑟2 dr
• The probability of finding the electron at different
radial distances r from the nucleus is:
• Probability (P) = 4𝜋𝑟2 [𝑅𝑛, 𝑙 𝑟 ]2 2.6.4
• Equation 2.6.4 is usually referred to as the radial
distribution function.
• A plot of this probability function against distance
from the nucleus as shown in Figure 2.11
• The curves shows that in any given atom the most
probable distance of an electron from the nucleus is at
a point r = 0, the probability function P = 0 implying
that no electron could be found at the nucleus.

•
 Nodal spheres
• Apart from the nucleus, there are surfaces at which the
probability of finding electron goes to zero.
• Such surfaces are called nodal spheres and is given as n-𝑙-1.
• Thus 2s and 3p have one nodal sphere each, while 3s has
2 nodal spheres, where the probability function P goes
through a maximum and it increases with increasing value
of n.
• The number of maxima (peaks) is given by 𝑛 − 𝑙
• Thus for n = 3, 𝑙 = 0 , 3s, we have 3-0 = 3 maxima
• 𝑙 = 1, 3p, we have 3-1 = 2 maxima
• 𝑙 = 2, 3d, we have 3-2 = 1 maxima.
Fig. 2.11 Radial distribution of the probability of an electron
versus the distance r, from the nucleus of hydrogen atom.
 ANGULAR WAVE FUNCTION:
• The angular part of the wave function 𝑌𝑙 , 𝑚𝑙(Θ, 𝜙),
depends
– on two quantum numbers 𝑙 and 𝑚𝑙 and
– on the angular distance Θ, from the north pole (z-axis) and
– the azimuthal angular distance 𝜙, from the reference
vertical plane.
• The angular part thus determines the shape of the
orbitals
• While the angular probability function shows how the
probability of locating electrons varies with direction.
• The type of orbital is determined by the 𝑙
quantum number:
• 𝑙 = 0 = s –orbital
• 𝑙 = 1 = p- orbital
• 𝑙 = 2 = d- orbital
• 𝑙 = 3 = f- orbital
• The number of orbitals of each type = 2𝑙 + 1
ELECTRONIC CONFIGURATION OF ATOMS.

• The arrangement of electrons in an atom is referred to

as electronic configuration or electronic structure.
• The four quantum numbers of electrons help us to
build up the electronic configurations of atoms.
• This arrangement of electrons is governed by certain
principles which are given below:
• Pauli Exclusion Principle:
• Aufbau Principle
• HUND’S RULE:
•
 Pauli Exclusion Principle:

• According to this principle no two electrons in

the same atom can have all the four quantum
numbers identical.
• If two electrons in an orbital should have the
same n, l, and ml values, their ms values will
differ (ms = + ½ or - ½).
• Consequently, an orbital can accommodate
only two electrons correspondingly to the two
allowed values of ms.
 Aufbau Principle

• Aufbau as a German word means building up.

• Thus according to the building up principle, the filling
of orbitals with electrons depends on two quantum
numbers viz:
– the principal quantum number n, and the azimuthal
quantum number l.
– n determines the energy level of an electron. It takes such
values as n=1, 2, 3, 4 ...
• The higher the value of n, the greater the energy.
• 𝑙 determines the type of orbital and takes such values
as 𝑙 = 0, 1, 2, 3,...,(n-1).
• The corresponding orbitals are s, p, d, f,... respectively.
• The energies of the orbital of the same energy
level (as determined by n) increases with
increasing values of 𝑙 .
• Thus the energy of s-orbital is less than that of p
which is in turn less than that of d i.e.
• s < p < d < f.
• The order of the filling of the orbitals is as shown
below:
• 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d <
5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p < 8s
• Electrons enters the orbitals in the order of
increasing energy in that orbitals with lowest
energy is filled first.
• The step-wise addition of electrons to the
orbital in the order of increasing energy is
known as Aufbau (building-up) principle.
 HUND’S RULE:

• When more than one degenerate orbitals are available,

electrons occupy separate orbitals with parallel spin
rather than pairing up with opposite spin in the same
orbital.
• Thus Hund’s rule of maximum multiplicity states that
electrons are distributed among degenerate orbitals in
a way that gives maximum number of parallel spin free
electrons.
• Following the above rules and/or principles which
governs the electronic arrangement in an atom, we can
now write the electronic configuration for the
elements in the periodic table.