Overview Pre-requisite knowledge

The topic is essentially about the

history of the atomic theory and the Laws of chemical combinations
development of the atomic structure.
Law of conservation of mass
The focus shall be on qualitative
treatment of the contributions of a
number of scientist to the Law of multiple proportions
determination of the structure of the
atom. Dalton’s atomic theory
A quantitative treatment of some
selected contributions shall be
undertaken as we proceed.
EXPECTED LEARNING
OUTCOMES
At the end of this topic students are expected to be able to:

• State the contribution of each scientists to the

development of the structure of the atom.
• Draw the various models of the atom.
• Write, define parameters, and solve problems with
the following relations: Einstein equation of
photoelectric effect, Rydberg formula, Broglie
equation.
• Define the number of expected spectra line from
electron transitions from a given energy level in a
hydrogen atom.
CHM 111 (General Physical Chemistry) 2
 GREEK PHILOSOPHERS

The ideal about the atom

was an abstract thought of
by the ancient Greek
Leucippus
philosophers, Leucippus first half of 5th century BC

and Democritus. They

believed that atoms
existed, but they had no
idea as to their nature.
CHM 111 (General Physical Chemistry)
Democritus3
460 - 370 BC
 JOHN DALTON

 John Dalton proposed a modernJohn Dalton

1766 - 1844
atomic model based on
experimentation and not on pure
reason.
 Dalton's atomic theory was based
on the assumption that atoms are
tiny indivisible entities, with each
chemical element consisting of its
own characteristic atoms.
CHM 111 (General Physical Chemistry) 4
 Limitations of Dalton’s theory
 Although Dalton’s atomic theory is a major
landmark in the history of the atomic structure,
however at that level of the atomic theory many
questions were left unanswered.
 These include identified phenomena such as
Electrolysis, Photoelectric effect, Isotopy,
Radioactivity, etc.
 The answers to these and many other fascinating
questions in chemistry are supplied by our modern
understanding of the nature of atoms.
The big challenge is how can something
as small as an atom be studied?
CHM 111 (General Physical Chemistry) 5
 Evolution of atomic structure
1896: J.J. Thomson’s discovery of the electrons
and the protons.

1909: Rutherford’s nuclear atom

1913: Mosley’s determination of atomic number

1913: Bohr atom

1932: Chadwick’s discovery of the neutron

CHM 111 (General Physical Chemistry) 6

 Discharge tube experiments
The most convincing evidence for the existence
of electrons came from experiments using
cathode-ray tubes.
In 1897, J. J. Thompson devised the
Cathode Ray xperiment.  Thompson
found that all metals he tested, when
used as the cathode in his high
voltage Cathode Ray tube, emitted
identical particles that were
attracted to the positive plate of the
voltage source.  He was able to
determine the charge to mass
ratio of these fundamental,
negatively charged particles, which
were later called electrons. 

CHM 111 (General Physical Chemistry) 7

Cathode-ray tubes
J. J. Thompson model of the Atom

Plum pudding model

CHM 111 (General Physical Chemistry) 8

Rutherford Scattering Experiment

CHM 111 (General Physical Chemistry) 9

 Rutherford Model
Based on the observations from the experiment,
Rutherford proposed a model of the atom called the
nuclear atom. According to it:
•Atom has a tiny dense central core (nucleus) which
contains practically the entire mass of the atom,
leaving the rest of the atom almost empty.
•The entire positive charge of the atom is located on
the nucleus, while electrons were distributed in vacant
space around it.
•The electrons were moving in orbits or closed circular
paths around a positively charged nucleus, like planets
orbiting the sun.
CHM 111 (General Physical Chemistry) 10
 Although the model is
Electrons
Nucleus consistent with the
experiment, however it
contradicts the then existing
knowledge (classical
electromagnetic theory).
Hence the model is faced
with the challenge of
explaining its stability. The
new questions begging for
answers are :

What keeps like charged

particles (protons)
together in the very small
Rutherford’s Model of the Atom nucleus ?

How do we explain the

stability of the electron
orbiting round the nucleus
(massive positively charged
centre)?
CHM 111 (General Physical Chemistry) 11
 The neutron
Rutherford theorized about the existence of
neutrons, which could somehow compensate
for the repulsive effect of the positive charges
of protons by causing an attractive nuclear
force and thus keeping the nuclei from
breaking apart. This was later discovered by
James Chadwick, the particle has no electric
charge as suggested by Rutherford.

CHM 111 (General Physical Chemistry) 12

Quantum Theory and Bohr Atom
Niels Bohr’s pointed out that the old laws of physics
just did not work in the submicroscopic world of the
atom. His explanation is based on Planck’s quantum
theory and Rutherford’s atomic model. However, he
started with the following assumptions:
• An electron in an atom occupy a fixed stationary energy level.
• An electron in an atom revolve round its nucleus in a circular
orbit.
• An electron while in any energy level neither emits nor absorbs
radiation.
• An electron move from one energy level to another when it
absorbs or emits discrete amount of energy.

CHM 111 (General Physical Chemistry) 13

NIELS BOHR ATOMIC MODEL

CHM 111 (General Physical Chemistry) 14

 THE QUESTIONS
• The Particle-like Behavior of Light
Waves; Black-body radiation, the
photoelectric effect, the Compton effect.

• The Puzzling Stability of the Atom as

proposed by Rutherford
Why doesn't the electron fall into the
nucleus?
What is the origin of atomic spectra?
CHM 111 (General Physical Chemistry) 15
 Quiz Questions
1. Which scientist is credited with discovering the
negatively charge subatomic particle in the atom?
2. If an atom has an equal amount of Protons and
electrons, what will its’ charge be?
3. Which is the correct sequence of the scientists who
made major changes in the model of the atom?
1-J.J. Thomson, 2-John Dalton
3-Niels Bohr, 4-Ernest Rutherford
4. Ernest Rutherford discovered that the atom is….
5. Bohr's Planetary Model represented what?

CHM 111 (General Physical Chemistry) 16

 MODERN VIEW OF THE ATOM
Modern Atomic Theory

The electrical nature The interaction of matter with

of matter energy in the form of light

These studies led scientists to These studies led to a much more

recognize that atoms are detailed understanding of the
composed of more fundamental arrangements of particles in
particles and helped them to atoms. It became clear that the
describe the approximate arrangement of the particles
arrangements of these particles determines the chemical and
in atoms physical properties of each
element.
CHM 111 (General Physical Chemistry) 17
 Electromagnetic Radiations

The wavelength and the frequency are related to each other by

ν λ = speed of propagation of the wave or νλ = c
CHM 111 (General Physical Chemistry) 18
 Light as a wave
Continuous spectrum of white light

Dispersion of visible light by a prism

Light from a source of white light is passed through a
slit and then through a prism. It is spread into a
continuous spectrum of all wavelengths of visible
CHM 111 (General Physical Chemistry) 19
light.
 Visible Light

 Visible light is only a very small portion of

the electromagnetic spectrum.
 Some radiant energy has longer or shorter
wavelengths than our eyes can detect.
 The chart in the next slide shows the
approximate ranges of the electromagnetic
spectrum on a logarithmic scale. The lower
part shows the visible region on an
expanded scale.
 Note that wavelength increases as frequency
decreases. CHM 111 (General Physical Chemistry) 20
Electromagnetic spectrum

CHM 111 (General Physical Chemistry) 21

 Examples
Light near the middle of the ultraviolet region of the electro-
magnetic radiation spectrum has a frequency of 2.73 x 1016 s-1.
Yellow light near the middle of the visible region of the spectrum
has a frequency of 5.26 1014 s-1. Calculate the wavelength that
corresponds to each of these two frequencies of light.

CHM 111 (General Physical Chemistry) 22

Quantum Theory of Radiation
• In 1900, Max Planck studied the spectral lines
obtained from hot body radiations at different
temperatures.
• According to him, light radiation was produced
discontinuously by the molecules of the hot
body, each of which was vibrating with a
specific frequency which increased with
temperature.
• Thus Planck proposed a theory that a hot body
radiates energy not in continuous waves but in
small units of waves (small packets, or
"quanta" of energy.
Max Planck suggests that radiation is quantized
(it comes in discrete amounts).
CHM 111 (General Physical Chemistry) 23
The energy of a photon of light is given by Planck’s
equation: E =hν    or E = hc/λ

E – energy of photon
h – Planck constant = 6.6260755 x 10-34 Js
ν – frequency
c - velocity of light = 3.00 x 108 m s-1
Example:
Calculated the wavelengths of ultraviolet light of frequency 2.73 x10 16 s-1 and of yellow
light of frequency 5.26 x 1014 s-1. Calculate the energy, in joules, of an individual photon
of each. Compare these photons by calculating the ratio of their energies.

A photon of light near the middle of the ultraviolet

region is more than 51 times more energetic than a
CHM 111 (General Physical Chemistry) 24
photon of light near the middle of the visible region.
 Quantitization of energy

E2 E2

∆E = E1 - E2 = hν ∆E = E2 - E1 = hν

E1 E1

Absorption Emission

h = 6.63 x 10-34 J s

CHM 111 (General Physical Chemistry) 25

 Photoelectric Effect
Most commonly observed phenomena with light can be explained
by waves. But the photoelectric effect suggested a particle nature
for light. It refers to the emission, or ejection, of electrons from
the surface of, generally, a metal in response to incident light. This
phenomenon was explained by Albert Einstein in 1905 using
Planck’s quantum hypothesis.

CHM 111 (General Physical Chemistry) 26

Photoelectric Effect contd.
 Einstein explained that increasing the
intensity of the incident radiation would
cause greater numbers of electrons to be
ejected, but each electron would carry the
same average energy because each incident
photon carried the same energy.
 This assumes that the dominant process
consists of individual photons being
absorbed by and resulting in the ejection of a
single electron.
 Likewise, in Einstein's model, increasing the
frequency, rather than the intensity, of the
incident radiation would increase the average
energy of the emitted electrons.
CHM 111 (General Physical Chemistry) 27
 Ephoton = Ework function + K.E (ejected electron)

hν = hνo + (½)mv2
hν = hνo + eVs
Where ν – frequency of the photon in Hz or per second
νo – threshold frequency
m – mass of electron

v - velocity of ejected electron

CHM 111 (General Physical Chemistry) 28

 ATOMIC SPECTRA (line spectrum)

The light emitted by a sample of excited hydrogen atoms or adsorbed

unexcited hydrogen atoms (or any other element) can be passed
through a prism and separated intoPhysical
CHM 111 (General certain discrete wavelengths.
Chemistry) 29
CHM 111 (General Physical Chemistry) 30
 Hydrogen atom spectra lines
 The spectra lines of hydrogen atom had been
measured by different scientists at different time.
 Surprisingly, the various spectra data of hydrogen
obeyed a mathematical relation:

ere R is 1.097 x 107 m-1 and is known as the Rydberg constant.

The n’s are positive integers, and n1 < n2.

CHM 111 (General Physical Chemistry) 31

 Series n1 n2 Region

Lyman 1 2,3,4,…,∞ Ultraviolet

Balmer 2 3,4,5,…,∞ Visible

Paschen 3 4,5,6,…,∞ Infrared

Brackett 4 5,6,7,…,∞ Infrared

Pfund 5 6,7,8,…,∞ Infrared

Humphreys 6 7,8,9,…,∞ Infrared

Why hydrogen emitted only those wavelengths at the different regions and why
the wavelengths obeyed the Rydberg formula was a complete mystery.

An explanation of the mystery was provided by Niels Bohr in 1913.

CHM 111 (General Physical Chemistry)
32
Ehi-Eromosele C.O.
 Bohr model of the hydrogen atom provided the
explanation for the stability of Rutherford ‘s atom
and a theoretical foundation for the Rydberg
formula.
From the above assumptions he derive a mathematical equations
describing the potential energies of electron in the orbits.
The radius, r, of the circular orbit. This is given by r = n2ao
where n is a positive integer (1, 2, 3, . . .) that tells which orbit is being
described and ao is the Bohr radius. Bohr was able to calculate the value of ao
from a combination of Planck’s constant, the charge of the electron, and the
mass of the electron as ao = 5.292 x 10-11 m = 0.5292 Å
The potential energy, E ,of an electron in an orbit is given by

CHM 111 (General Physical Chemistry) 33

 R – Empirical 109677 cm-1
R – Theoretical 109678 cm-1
Each line in the emission spectrum represents the difference
in energies between two allowed energy levels for the
electron. When the electron goes from energy level n2 to
energy level n1, the difference in energy is given off as a
single photon. The energy of this photon can be calculated
from Bohr’s equation for the energy, as follows:
E of photon = E2 - E1
∆E = Ef - Ei

CHM 111 (General Physical Chemistry) 34

CHM 111 (General Physical Chemistry) 35
CHM 111 (General Physical Chemistry) 36
CHM 111 (General Physical Chemistry) 37
 Example
Calculate the wavelength of light that corresponds to the transition of the
electron from the n=4 to the n=2 state of the hydrogen atom. Is the light
absorbed or emitted by the atom? Given that R = 2.18 x 10-18 J

Since the electron is "falling" from level 4 down to level 2, energy will be given
up and manifested as emitted electromagnetic radiation:

∆E = (2.18 x 10-18 J)((1/16)-(1/4)) = -4.09 x 10-19 J (light is emitted)

4.09 x 10-19 J = (6.63 x 10-34 Js) * (ν)

6.17 x 1014 s-1 = ν

λ = (3.00 x 108 m s-1)/CHM

(6.17 x 1014 s-1) = 4.87 x 10-7m = 487 nm
111 (General Physical Chemistry) 38
Although the Bohr theory satisfactorily explained the
spectra of hydrogen and of other species containing
one electron (He+, Li2+, etc.), the wavelengths in the
observed spectra of more complex species could not
be calculated.

High resolution hydrogen spectrum contain fine line

which could not be accounted for by Bohr’s theory.

Some chemical bonding phenomena are also not

explainable using Bohr’s theory.

CHM 111 (General Physical Chemistry) 39

 Atomic no

From the time of

Mendeleev, the order of
the elements had been
determined mostly by
increasing atomic mass.
It was the work of Harry
(Henry Gwyn-Jefferies)
Moseley in the analysis of
the lines in the X-ray
spectra of the elements
that came the suggestion
that atomic number, the
Moseley's Modeling of X-ray Frequencies place of an element on
the periodic table.
CHM 111 (General Physical Chemistry) 40
 Louis de Broglie
• Louis de Broglie argued that light have wave
properties and it had also been shown to exhibit
particle-like properties by phenomenon such as
photoelectric effect.
• Therefore all particles should also behave as a wave.
He proved theoretically that in fact all particles
exhibited wave like properties to some degree.

where p - momentum of the particle

h - Planck constant
λ– wave length
CHM 111 (General Physical Chemistry) 41
 Example
(a) Calculate the wavelength in meters of an electron traveling
at 1.24 x 107 m/s. The mass of an electron is 9.11 x 10-28 g.
(b) Calculate the wavelength of a baseball of mass 0.525 kg
traveling at 9.25 m s-1.

CHM 111 (General Physical Chemistry) 42

 Implication of Louis de Broglie
postulate
It implies that the electron so far is been
treated as a particle is also a wave. We
have only been looking at one side of a two
sided coin. A complete description of an
electron should incorporate both particle
and wave like properties.

CHM 111 (General Physical Chemistry) 43

 Clinton Davission
and Lester German
demonstrated the
wave property of
the electron with
Diffraction
experiment

Electron Diffraction Pattern

CHM 111 (General Physical Chemistry) 44

 Werner Heisenberg
Uncertainty principle

It is impossible to determine accurately both the

momentum and the position of an electron (or any
other very small particle) simultaneously.

CHM 111 (General Physical Chemistry) 45

This further complicate the picture
about the electron. It introduces a
probability concept to the location of
an electron. Thus, we can no longer be
sure of the exact position of an
electron as earlier proposed by Bohr.
We can only speak in terms of an area
in space where the probability of
locating an electron is high. This is
referred to as orbital.

CHM 111 (General Physical Chemistry) 46

 Schrodinger wave equation
Schrodinger treated the electron as a wave and
developed a mathematical equation to describe its wave-
like behavior. Schrodinger's equation related the amplitude
of the electron wave ,psi, to any point in space around the
nucleus. The Schrodinger equation looks like this:

Schrödinger’s equation and wave functions for one direction description

CHM 111 (General Physical Chemistry) 47
 Schrödinger’s equation and wave functions for three direction description

operator - a series of mathematical ste

where
is the Laplacian operator

is the wave function describing the displacement at any point along the wave. It is a mathematical
function that describes a wave-like shape

= is the Hamiltonian Operator

that describes the energy of the electronic system

CHM 111 (General Physical Chemistry) 48

This equation has been solved exactly only for one-
electron species such as the hydrogen atom and the
ions He+ and Li2+. Simplifying assumptions are
necessary to solve the equation for more complex
atoms and molecules.

The solution of the equation for the hydrogen

atom give rise to three quantum numbers
which describes the state of an electron in an
atom.

CHM 111 (General Physical Chemistry) 49

 Paul A. M. Dirac
Paul A. M. Dirac
(1902–1984)

In 1928, Paul A. M. Dirac (1902–1984) reformulated

electron quantum mechanics to take into account the
effects of relativity. This gave rise to a fourth quantum
number

The solutions of the Schrödinger and Dirac equations

for hydrogen atoms give wave functions, ψ , that
describe the various states available to hydrogen’s
single electron. Each of these possible states is
described by four quantum numbers.
CHM 111 (General Physical Chemistry) 50
The quantum numbers to designates the electronic arrangements
in all atoms, their so-called electron configurations. These
quantum numbers play important roles in describing the energy
levels of electrons and the shapes of the orbitals that describe
distributions of electrons in space.

Recall,

There are four quantum numbers, designated:

n, l, m, and s.

Each electron within an atom can be described by

a unique set of four quantum numbers.
CHM 111 (General Physical Chemistry) 51
1. QUANTUM NUMBER
The principal quantum number, n,
describes the main energy level, or
shell, an electron occupies. It may be any
positive integer:
n = 1, 2, 3, 4, . . .
The maximum number of electrons possible
in any one level is 2n2. Thus, in the first level (n =
1), there may be at most two electrons (2 x 12). In the
fourth energy level, there can be no more than 32
electrons (2 x 42) etc.
CHM 111 (General Physical Chemistry) 52
CHM 111 (General Physical Chemistry) 53
2.
• The angular momentum quantum number,
designates the shape of the region
in space that an electron occupies. Within a shell
(defined by the value of n, the principal quantum
number) different sub-levels or subshells are
possible, each with a characteristic shape.
• The angular momentum quantum number
designates a sub-level, or specific shape of atomic
orbital that an electron may occupy. This
number, l, may take integral values from 0 up to
and including (n - 1):
0, 1, 2, . . . , (n - 1)
CHM 111 (General Physical Chemistry) 54
Thus, the maximum value of l is (n - 1). We
give a letter notation to each value of l . Each
letter corresponds to a different sub-level
(sub-shell).
0, 1, 2, 3, 4, 5,. . . , (n- 1)
s p d f g h
In the first shell, the maximum value of l is
zero, which tells us that there is only an s
subshell and no p subshell. In the second
shell, the permissible values of l are 0 and 1,
which tells us that there are only s and p sub-
shells.
CHM 111 (General Physical Chemistry) 55
 3.
The magnetic quantum number, ml, designates
the specific orbital within a subshell. Orbitals
within a given subshell differ in their orientations in
space, but not in their energies. Within each subshell,
ml may take any integral values from –l through zero
up to and including +l:
ml = (-l), . . . , 0, . . . , (+l)
The maximum value of ml depends on the value of l.
For example, when l = 1, which designates the p
subshell, there are three permissible values of ml :
-1, 0, 1.
Thus, three distinct regions of space, called atomic
orbitals, are associated with a p sub-shell.
CHM 111 (General Physical Chemistry) 56
4.
The spin quantum number, ms, refers to the
spin of an electron and the orientation of the
magnetic field produced by this spin. For every set of
n, l, and ml values, ms can take the value +½ or -½:
ms = ± ½

•The values of n, l , and ml describe a particular

atomic orbital.
•Each atomic orbital can accommodate no more than
two electrons, one with ms = + ½ and another with
ms = - ½
CHM 111 (General Physical Chemistry) 57
Permissible Values of the Quantum Numbers Through n=4

CHM 111 (General Physical Chemistry) 58

 ATOMIC ORBITALS
An atomic orbital is a mathematical function that
describes the wave-like behavior of an electron in an
atom. This function can be used to calculate the
probability of finding any electron of an atom in any
specific region around the atom's nucleus. The term
"orbital" has become known as either the
"mathematical function" or the "region" generated
with the function. Specifically, atomic orbitals are
the possible quantum states of an individual electron
in the electron cloud around a single atom, as
described by the function.

CHM 111 (General Physical Chemistry) 59

For each solution to the quantum mechanical equation, we can
calculate the electron probability density (sometimes just
called the electron density) at each point in the atom.

This is the probability of finding an electron at that point. It

can be shown that this electron density is proportional to r2ψ2,
where r is the distance from the nucleus.

An electron cloud surrounding an atomic nucleus. The electron density drops off
rapidly but smoothly as distance from the nucleus increases.
CHM 111 (General Physical Chemistry) 60
Plots of the electron density distributions associated with s orbitals. For any s orbital, this
plot is the same in any direction (spherically symmetrical). The sketch below each plot
shows a cross-section, in the plane of the atomic nucleus, of the electron cloud associated
with that orbital. Electron densityCHM
is proportional to rChemistry)
111 (General Physical ψ.
2 2 61
 (a) The relative directional character of a set of p orbitals.
(b) A model of three pCHM
orbitals (px, Physical
111 (General
py, and pz) of a single set of orbitals.
Chemistry) 62
Spatial orientation of d orbitals. Note that the lobes of the dx 2-y2 and dz2 orbitals lie along the
axes, whereas the lobes of the others lie along diagonals between the axes.
CHM 111 (General Physical Chemistry) 63
Relative directional character of f orbitals. The seven orbitals are shown within cubes as an aid
to visualization
CHM 111 (General Physical Chemistry) 64
CHM 111 (General Physical Chemistry) 65
 ELECTRON CONFIGURATIONS
The electronic arrangement of an isolated atom in its lowest energy, or
unexcited, state is referred as the ground state electron configuration.
Electron configurations for the elements are determined by experiment. In
describing ground state electron configuration, the guiding idea is that the
total energy of the atom is as low as possible. To determine these
configurations, we use the follwing guides:

Aufbau Principle : Electrons are assigned to orbitals in order increasing

energy
This can be broken down into two general rules which help us to predict electron
configurations

CHM 111 (General Physical Chemistry) 66

The usual order of filling (Aufbau order) of the orbitals of an atom
CHM 111 (General Physical Chemistry) 67
 An aid to remembering the
usual order of filling of
atomic orbitals. Write each
shell (value of n) on one
horizontal line, starting
with n = 1 at the bottom.
Write all like subshells
(same values) in the same
vertical column. Subshells
are filled in order of
increasing (n + l ). When
subshells have the same (n
+ l ), the subshell with the
lower n fills first. To use
the diagram, we follow the
diagonal arrows in order,
reading bottom to top.

CHM 111 (General Physical Chemistry) 68

Pauli Exclusion Principle: No two electrons in an atom may have identical
sets of four quantum numbers.

Hund’s Rule: Electrons occupy all the orbitals of a given subshell singly
before pairing begins. These unpaired electrons have
parallel spins.

CHM 111 (General Physical Chemistry) 69

CHM 111 (General Physical Chemistry) 70
CHM 111 (General Physical Chemistry) 71
CHM 111 (General Physical Chemistry) 72
 Example
Write an acceptable set of four quantum numbers for each
electron in a nitrogen atom.

73
CHM 111 (General Physical Chemistry)
 PERIODIC TABLE
One of the most well known and ubiquitous symbols of
modern science in general and chemistry in particular
is the Periodic Table of the Elements. The modern
periodic table has been almost 300 years in the
making. Early efforts to group elements produced the
tables of Geoffroy (1718) and Lavoisier (1787). The
atomic theory formulated by Dalton in the early 1800s
provided chemists with a solid basis to clasify
elements, and the theory stimulated vigorous
experimentation that culminated in the development
of the modern form of the periodic table in 1869.
CHM 111 (General Physical Chemistry) 74
In our modern periodic table of elements, elements
are arranged in columns and rows. As its name
implies, the modern table is periodic in nature,
meaning that elements are placed in it based on
their shared and recurring (periodic) characteristics.
Periodicity of element properties is found to be
strongest down columns of the table. Primary
among these periods is that of the 6 noble (or inert)
gases which populate the far right column of the
table. The property shared by the inert gases is a lack
of reactivity ensuing from their inability to gain or
lose electrons.

CHM 111 (General Physical Chemistry) 75

In the modern perodic table, the elements are
arranged in order of increasing number of
protons.

The atomic number of an element is the

number of protons in the nucleus and the
number of electrons in a neutral atom.

The atomic weight increases with increasing

number of protons and neutrons.

The atomic weight is the average weight of all

the isotopes of that element (the average of
the natural abundance x mass number).

CHM 111 (General Physical Chemistry) 76

THE PERIODIC TABLE AND ELECTRON
CONFIGURATIONS

CHM 111 (General Physical Chemistry) 77

CHM 111 (General Physical Chemistry) 78
It is divided into metals (left side), nonmetals (right
side), and metalliods.
metalliods Metals are on the left side while
the nonmetals are toward the upper right of the table.
Metalloids have properties of metals and nonmetals
and are found bordering the diagonal line.

It is arranged in rows (across) in order of increasing

energy levels of valence electrons (called periods).
periods
The period number represents the energy level for
that row.
is arranged in columns (down) in order of similar
orbitals for the valence electrons (called groups).
groups

The elements are represented by one or two letter

symbols, which have some correlation to the element
name.
CHM 111 (General Physical Chemistry) 79
CHM 111 (General Physical Chemistry) 80
 Metals Nonmetals
• Located on the left side of the • Located on the right side of
periodic table the periodic table
• Tends to lose electrons to • Tends to gain electrons to
form cations form anions
• Has low ionization energies & • Has high ionization energies
electronegativity values & electronegativity values
• Forms compounds with • Forms compounds with
nonmetals but not other both metals and nonmetals
metals • Poor conduction of heat
• Good conduction of heat and and electricity
electricity • Non-lustrous & brittle or
• Lustrous & malleable solids gaseous
excepts Hg which is a liquid • Non-ductile
• Ductile
CHM 111 (General Physical Chemistry) 81
 Sub-Classes of Metals
• Alkali metals - (lithium, sodium, potassium,
rubidium and cesium) - soft, low melting points,
react with water to liberate hydrogen, form 1:1
compounds with chlorine.
• Alkaline earths - (beryllium, magnesium, calcium,
strontium, barium and radium) - react in a 1:2
ratio with chlorine.
• Transition metals - (e.g. iron, copper, silver, gold,
tungsten and cobalt) - structural metals
• Metalloids - (antimony, arsenic, boron, silicon and
tellurium) - intermediate between metals and
nonmetals.
CHM 111 (General Physical Chemistry) 82
 Non-Metals
• Chalcogens - (oxygen, sulfur, selenium and
tellurium) - form 1:1 compounds with alkaline-
earths, but 2:1 compounds with alkali-metals.
• Halogens - (fluorine, chlorine, bromine and
iodine) - highly reactive and form 1:1
compounds with alkali-metals.
• Noble gases - (helium, neon, argon, krypton,
radon) - virtually inert to chemical reactions.

CHM 111 (General Physical Chemistry) 83

 Groups in the Periodic Table
Main Group Elements (Vertical Groups)
Group IA - Alkali Metals
Group IIA - Alkaline Earth Metals
Group IIIA - Boron Family
Group IVA - Carbon Family
Group VA - Nitrogen Family
Group VIA - Oxygen Family (Calcogens)
Group VIIA - Halogens
Group VIIIA - Noble Gases
Other Groups ( Vertical and Horizontal Groups)
Group IB - 8B - Transition Metals
Period 6 Group - Lanthanides (Rare Earth Elements)
Period 7 Group - Actinides
CHM 111 (General Physical Chemistry) 84
 The Periodic Table of the Elements
H He
Li Be B C N O F Ne
NaMg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr NbMo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Rf Du Sg Bo HaMe

Ce Pr Nd PmSmEu Gd Tb Dy Ho Er TmYb Lu
Th Pa U Np PuAmCmBk Cf Es FmMd No Lr

The Alkali Metals The Halogens

The Alkaline
Earth Metals The Noble Gases
CHM 111 (General Physical Chemistry) 85
 The Periodic Table of the Elements
H He
Li Be B C N O F Ne
NaMg Al Si P S Cl Ar
K Ca Sc Ti V CrMn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Rf Du Sg Bo Ha Me

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np PuAmCm Bk Cf Es FmMd No Lr

Boron family Nitrogen family

Carbon Family Oxygen Family

CHM 111 (General Physical Chemistry) 86
 The Periodic Table of the Elements
H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V CrMn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr NbMo Tc Ru Rh PdAg Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac Rf Du Sg Bo Ha Me
The Transition Metals

Ce Pr Nd PmSm Eu Gd Tb DyHo Er TmYb Lu

Th Pa U Np PuAmCmBk Cf Es FmMd No Lr

Lanthanides: The
The Actinides
Rare Earth Elements
CHM 111 (General Physical Chemistry) 87
• The periodic table is also divided into "blocks" blocks
which represent the orbital the electron
occupies; s, p, d, and f.
• It is read left to right; 1s, 2s, 2p, 3s, 3p, 4s....
• It is arranged as representative elements (s and
p block elements), transition metals (d block
metals), lanthanides and actinides (f block
metals).
• It is arranged in order of increasing energy of
the subshells; the lowest energy level is always
filled first.
• The noble gases are unreactive since they have
a completely filled shell and are the lowest in
energy. CHM 111 (General Physical Chemistry) 88
 Periodic Table and Electron Configurations
• Build-up order given by position on periodic table; row by row.
• Elements in same column will have the same outer shell electron
configuration.

CHM 111 (General Physical Chemistry) 89

CHM 111 (General Physical Chemistry) 90
 PERIODIC LAW
The properties of the elements are periodic
functions of their atomic numbers.
When the properties of the elements are plotted
against atomic number, a periodic variation in
their properties was observed.
• The boundaries of the periods seem to be marked
by the appearance of the noble gases at 2, 10, 18, 36,
54 and 86 amu.
• The variations in both melting point and atomic
radius seem to correlate (inversely).
• The different element classifications also appear
cyclically in this periodic variation. 91
CHM 111 (General Physical Chemistry)
The periodic table is not only an organizing principle,
but it has (had) predictive power as well.

As valuable as the periodic table is, the explanation of

its organization was not obvious. It was not until the
advent of quantum mechanics that the electronic
structure of the atoms could be used to explain the
periodic variation in properties.

CHM 111 (General Physical Chemistry) 92

 Periodic trends in atomic properties
The periodic table demonstrates the
trends in the following atomic
properties of the elements.
• Metallic properties
• Atomic radii
• Effective nuclear charge
• Ionization energy
• Electron affinity
• Electronegativity
• Ionic radii
• Magnetic properties
CHM 111 (General Physical Chemistry) 93
 Metallic properties
Metallic character increases down the group
but decreases along the periods. This
cumulates into diagonal division of the
periodic table into metal and non-metals.
The elements along the diagonal have
properties that are intermediate between
that of metals and non-metals

CHM 111 (General Physical Chemistry) 94

 ATOMIC RADII
Within a family (vertical group on
the periodic table)of representative
elements, atomic radii increase
from top to bottom as electrons are decreases

added to shells farther from the

i
nucleus. As we move from left to n
right across a period in the c
r
periodic table, atomic radii of e
a
representative elements decrease s
as a proton is added to the nucleus e
s
and an electron is added to a
particular shell.CHM 111 (General Physical Chemistry) 95
CHM 111 (General Physical Chemistry) 96
 Effective nuclear charge
The effective nuclear charge, Zeff, experienced
by an electron in an outer shell is less
than the actual nuclear charge, Z. This is because the
attraction of outer-shell electrons by the nucleus is
partly counterbalanced by the repulsion of these
outer-shell electrons by electrons in inner shells. We
say that the electrons in inner shells screen, or shield,
electrons in outer shells from the full effect of the
nuclear charge. This concept of a screening,
or shielding, effect helps us understand many
periodic trends in atomic properties.
CHM 111 (General Physical Chemistry) 97
 IONIZATION ENERGY
The first ionization energy (IE1), also called
first ionization potential, is the minimum
amount of energy required to remove the most
loosely bound electron from an isolated gaseous
atom to form an ion with a +1 charge.
It is the amount of energy increases
d The first
required to remove the first e
c
ionization
energy
electron from an atom as r
e
generally
increases
demonstrated below: a
s across a
e period and
M(g)  M(g)+ + e- s decreases
down a
group.
CHM 111 (General Physical Chemistry) 98
CHM 111 (General Physical Chemistry) 99
First ionization energies

CHM 111 (General Physical Chemistry) 100

 ELECTRON AFFINITY
The electron affinity (EA) of an element may
be defined as the amount of energy absorbed when
an electron is added to an isolated gaseous atom
to form an ion with a -1 charge.

Elements with very negative electron affinities gain

electrons easily to form negative ions (anions).
CHM 111 (General Physical Chemistry)
A plot of electron affinity versus atomic number for the first 20 elements.
CHM 111 (General Physical Chemistry) 102
 IONIC RADII
Atoms of the element forms ions in the same manner and charge
magnitude. Some lose electrons to form cation while others gain
electrons to form anion. Hence, comparison of radii is not a simple
issue as in the case of atomic radii. Sometimes we compare atoms to
their ions, atoms or ions that are vertically or horizontally positioned
on the periodic table, or isoelectronic species.

CHM 111 (General Physical Chemistry) 103

The following guidelines are often considered in the order given.
1.Simple positively charged ions (cations) are always
smaller than the neutral atoms from which they are formed.
2.Simple negatively charged ions (anions) are always
larger than the neutral atoms from which they are formed.
3.The sizes of cations decrease from left to right across
a period.
4.The sizes of anions decrease from left to right across a
period.
5.Within an isoelectronic series, radii decrease with
increasing atomic number because of increasing nuclear
charge.
6.Both cation and anion sizes increase going down a
group.

CHM 111 (General Physical Chemistry) 104

Atomic radii of the A group (representative) elements and the noble gases, in
angstroms, compare with atomic radii which increase going down a group
because electrons are being added to shells farther from the nucleus. Atomic
radii decrease from left to right within a given period owing to increasing
effective nuclear charge. CHM 111 (General Physical Chemistry) 105
CHM 111 (General Physical Chemistry) 106
 ELECTRONEGATIVITY
The electronegativity (EN) of an element is a measure of
the relative tendency of an atom to attract electrons to itself
when it is chemically combined with another atom. Elements
with high electronegativities (nonmetals) often gain electrons to
form anions. Elements with low electronegativities (metals) often
lose electrons to form cations.
increases
For the representative
The
elements, electronegativities d electro-
e
usually increase from left to c
negativity
generally
right across periods and r increases
decrease from top to bottom e across a
a period and
within groups. s decreases
e down a
CHM 111 (General Physical Chemistry) group.
CHM 111 (General Physical Chemistry) 108
 Magnetic Properties
Although an electron behaves like a tiny magnet, two
electrons that are opposite in spin cancel each other.
Only atoms with unpaired electrons exhibit magnetic
susceptibility.
– A paramagnetic substance is one that is
weakly attracted by a magnetic field, usually the
result of unpaired electrons.
– A diamagnetic substance is not attracted by a
magnetic field generally because it has only
paired electrons.

CHM 111 (General Physical Chemistry) 109

Diagram of an apparatus for measuring the paramagnetism of a substance.
The tube contains a measured amount of the substance, often in solution.
(a)Before the magnetic field is turned on, the position and mass of the sample
are determined.
(b) When the field is on, a paramagnetic substance is attracted into the field.
(c) A diamagnetic substance would be repelled very weakly by the field.
CHM 111 (General Physical Chemistry) 110
The metals of the iron triad (Fe, Co, and Ni) are the
only free elements that exhibit ferromagnetism.
This property is much stronger than
paramagnetism; it allows a substance
to become permanently magnetized when placed in a
magnetic field. This happens as randomly oriented
electron spins align themselves with an applied field.
To exhibit ferromagnetism, the atoms must be within
the proper range of sizes so that unpaired electrons
on adjacent atoms can interact cooperatively with one
another, but not to the extent that
they pair.

CHM 111 (General Physical Chemistry) 111

 NUCLEAR CHEMISTRY
Chemical properties are determined by electron
distributions and are only indirectly influenced by
atomic nuclei. Until now, we have discussed ordinary
chemical reactions, so we have focused on electron
configurations. Nuclear reactions involve changes in
the composition of nuclei. These extraordinary
processes are often accompanied by the release of
tremendous amounts of energy and by transmutations
of elements. Some differences between nuclear
reactions and ordinary chemical reactions follow.

CHM 111 (General Physical Chemistry) 112

CHM 111 (General Physical Chemistry) 113
 The Nucleus
The nucleus is only a minute fraction of the total
volume of an atom, yet nearly all the mass of an atom
resides in the nucleus. Thus, nuclei are extremely
dense. It has been shown experimentally that nuclei
of all elements have approximately the same density,
2.4 x 1014 g/cm3.

CHM 111 (General Physical Chemistry) 114

 NEUTRON–PROTON RATIO AND
NUCLEAR STABILITY
Physicists have since detected many very short-lived subatomic
particles (in addition to protons, neutrons, and electrons) as
products of nuclear reactions. The functions are not entirely
understood, but it is now thought that they help to overcome
the proton–proton repulsions and to bind nuclear particles
(nucleons) together.

CHM 111 (General Physical Chemistry) 115

A plot of the number of neutrons versus the number of protons in stable nuclei.
As atomic number increases, the N/Z ratio (the decimal fractions) of the stable
nuclei increases. The stable nuclei are located in an area known as the band
of stability. Most radioactive nuclei occur outside this band.
CHM 111 (General Physical Chemistry) 116
 NUCLEAR STABILITY AND BINDING ENERGY
Experimentally, we observe that the masses of atoms other
than 1H are always less than the sum of the masses of their
constituent particles. We now know why this mass deficiency
occurs. We also know that the mass deficiency is in the nucleus
of the atom and has nothing to do with the electrons; however,
because tables of masses of isotopes include the electrons, we
shall also include them.

The mass deficiency, ∆m, for a nucleus is the

difference between the sum of the masses of electrons,
protons, and neutrons in the atom (calculated mass) and the
actual measured mass of the atom.

∆m = (sum of masses of all e-, p+, and n0) (actual mass of atom)
CHM 111 (General Physical Chemistry) 117
EXAMPLE
Calculate the mass deficiency for chlorine-35 atoms in amu/atom
and in g/mol atoms. The actual mass of a chlorine-35 atom is
34.9689 amu.

CHM 111 (General Physical Chemistry) 118

 What has happened to the mass
represented by the mass deficiency?
In 1905, Einstein set forth the Theory of Relativity. He stated
that matter and energy are equivalent. An obvious corollary is
that matter can be transformed into energy and energy into
matter. The transformation of matter into energy occurs in the
sun and other stars. It happened on earth when controlled
nuclear fission was achieved in 1939. The reverse
transformation, energy into matter, has not yet been
accomplished on a large scale. A mass deficiency represents the
amount of matter that would be converted into energy
and released if the nucleus were formed from initially separate
protons and neutrons. This energy is the nuclear binding
energy, BE.

CHM 111 (General Physical Chemistry) 119

EXAMPLE
Calculate the nuclear binding energy 35Cl in (a) kilojoules per mole of Cl atoms, (b)
kilojoules per gram of Cl atoms, and (c) megaelectron volts per nucleon. Given that
1 megaelectron volt (MeV) 1.60 x 1013 J and 1 joule (J) 1 kgm2/s2

CHM 111 (General Physical Chemistry) 120

DECAY MODES

CHM 111 (General Physical Chemistry) 121

 NEUTRON-RICH NUCLEI (ABOVE THE BAND OF STABILITY)

Nuclei in this region have too high a ratio of neutrons to protons. They undergo
decays that decrease the ratio. The most common such decay is beta emission. A
beta particle is an electron ejected from the nucleus when a neutron is converted
into a proton.

Thus, beta emission results in an increase of one in the number of protons (the
atomic number) and a decrease of one in the number of neutrons, with no change in
mass number. Examples of beta particle emission are

The sum of the mass numbers on each side of the first equation is 228, and the sum
of the atomic numbers on each side is 88. The corresponding sums for the second
equation are 14 and 6, respectively.

CHM 111 (General Physical Chemistry) 122

 NEUTRON-POOR NUCLEI (BELOW THE BAND OF STABILITY)
Two types of decay for nuclei below the band of stability are positron emission or electron
capture (K capture). Positron emission is most commonly encountered with
artificially radioactive nuclei of the lighter elements. Electron capture occurs most often with
heavier elements. A positron has the mass of an electron but a positive charge. Positrons are
emitted when protons are converted to neutrons.

Thus, positron emission results in a decrease by one in atomic number and an increase by one
in the number of neutrons, with no change in mass number. The same effect can be
accomplished by electron capture (K capture), in which an electron from the K shell (n 1) is
captured by the nucleus.

Some nuclides, such as 22 Na, undergo both electron capture and positron emission.

Some of the neutron-poor nuclei, especially the heavier ones, increase their neutron-to proton
ratios by undergoing alpha emission. Alpha particles are helium nuclei, 4He, consisting
of two protons and two neutrons. Alpha emission also results in an increase of the neutron-to-
proton ratio. An example is the alpha emission of lead-204.

123
CHM 111 (General Physical Chemistry)
NUCLEI WITH ATOMIC NUMBER GREATER THAN 83

All nuclides with atomic number greater than 83 are beyond the band of
stability and are radioactive. Many of these decay by alpha emission.

The decay of radium-226 was originally reported in 1902 by Rutherford and

Soddy. It was the first transmutation of an element ever observed. A few
heavy nuclides also decay by beta emission, positron emission, and electron
capture. Some isotopes of uranium (Z = 92) and elements of higher atomic
number, the transuranium elements, also decay by spontaneous
nuclear fission. In this process a heavy nuclide splits into nuclides of
intermediate mass and neutrons.

CHM 111 (General Physical Chemistry) 124

 RATES OF DECAY AND HALF-LIFE
Radionuclides have different stabilities and decay at
different rates. Some decay nearly completely in a
fraction of a second and others only after millions of
years. The rates of all radioactive decays are
independent of temperature and obey first-order
kinetics.

a is always 1 for radioactive decay

CHM 111 (General Physical Chemistry) 125

CHM 111 (General Physical Chemistry) 126
 Half-life t1/2
For a first-order process, t1/2 is given by the equation

EXAMPLE
The “cobalt treatments” used in medicine to arrest certain types of cancer
rely on the ability of gamma rays to destroy cancerous tissues. Cobalt-60
decays with the emission of beta particles and gamma rays, with a half-life
of 5.27 years.

How much of a 3.42-g sample of cobalt-60 remains after 30.0 years?

CHM 111 (General Physical Chemistry) 127

CHM 111 (General Physical Chemistry) 128
DISINTEGRATION SERIES

CHM 111 (General Physical Chemistry) 129

Assignment

CHM 111 (General Physical Chemistry) 130