ATOMIC

STRUCTURE
Unit 1
Chemistry
 OBJECTIVES

• discuss the process of theoretical change with respect to Dalton's

atomic theory;
• describe the structure of the atom;
• define the following terms:
(a) mass number;
(b) isotopes; and,
(c) relative atomic and isotopic masses based on the carbon-12 scale.
 OBJECTIVES CONT'D

• explain the phenomenon of radioactivity

• cite the use of radioisotopes;
• calculate the relative atomic mass of an element, given isotopic masses
and abundances;
• explain how data from emission spectra provide evidence for discrete
energy levels within the atom;
• describe the atomic orbitals; s, p and d orbitals
THE STRUCTURE OF THE ATOM

• Over centuries many theories were developed but today

only a few remain valid. One of the most “talked-about”
theories was the one made by John Dalton, a physicist,
meteorologist and a chemist. One of the main reasons why
his work is so popular today is because some of his
discoveries have helped in the development of the modern
atomic theory. There are however cases where his theory is
a little different from modern theories.
 DALTON'S ATOMIC THEORY

•All matter is made of atoms. Atoms are indivisible

and indestructible.
•All atoms of a given element are identical in mass
and properties
•Compounds are formed by a combination of two or
more different kinds of atoms.
•A chemical reaction is a rearrangement of atoms
 CASES WHERE DALTONS THEORY IS
DIFFERENT

John Dalton’s theory stated that atoms of the same element

have identical masses, but modern theories have proved
that atoms of the same element can have different
masses, these atoms are called Isotopes however they do
have the same chemical properties.
• In modern research it was discovered that atoms can be
destroyed by nuclear reactions but not by chemical
reactions.
 TIMELINE FOR CHANGE IN
ATOMIC THEORY

• Democritus, 460 BC   Came up with the idea of

atoms
• John Dalton, 1807- After the idea of atoms was
dismissed for over 2000 years, he reintroduced the
idea of atoms and through many experiments he
proved the existence of atoms.
 JOSEPH .J.THOMPSON, 1897

• Stated that positively charged substances were

distributed uniformly over the surface of the atom
containing electrons embedded within them
• DISCOVERED ELECTRONS
• Electrons are negatively charged particles
• Also discovered the relative mass of electrons
 ERNEST RUTHERFORD, 1909

• From J.Thompson’s model and through his own

experiments he was able to determine the true
model of the atom. Instead of the positively
charged particles being distributed over the atom
they were gathered together in the nucleus.
• Discovery and naming of the proton and
essentially the nucleous
GEIGER-MARSDEN EXPERIMENT
 SIMULATION OF THE
EXPERIMENT

https://phet.colorado.edu/sims/html/ruthe
rford-scattering/latest/rutherford-scatteri
ng_en.html
 E. GOLDSTEIN, 1886-1887

Eugene Goldstein was born in 1850 in Poland Died

December 25, 1930 in Berlin Germany
Goldstein's with cathode-ray and worked with anode
rays. He observed particles moving toward the
cathode (negative terminal) to suggested the
presence of the proton -- a positively charged
particle.
 NIELS BOHR, 1913

He came up with these rules:

• Electrons can only orbit a fixed distance from the
nucleus.
• Atoms lose energy when electrons go from higher
energy to lower energy orbits and the opposite
happens from lower energy to higher energy
orbits.
 HENRY MOSELY, 1913

He suggested that there must be a

neutral particle in the atom, thus
prompting other scientist to
experiment, like James Chadwick.
 JAMES CHADWICK, 1932

• James Chadwick bombarded beryllium

atoms with alpha particles. An unknown
radiation was produced. Chadwick
interpreted this radiation as being composed
of particles with a neutral electrical charge
and the approximate mass of a proton.
 JAMES CHADWICK, 1932

• This particle became known as

the neutron. With the discovery of the
neutron, an adequate model of the
atom became available to chemist
 SUMMARY OF THEORY

• All atoms are composed of three important

particles : protons , neutrons and electrons
• All atoms have a small positive nucleus
surrounded by a much larger region of space in
which tiny electrons move continuously
• The positive charge of the nucleus is due to
positively charged protons.
 SUMMARY OF THEORY

• The nucleus also contains uncharged neutrons

which have virtually the same mass as protons
• Protons and neutrons are about 1840 times heavier
than electrons ( mass is from protons and neutrons)
• Positive charge on one proton is equal to the
negative charge on an electron ( atoms have equal
number of protons and electrons )
 VIDEOS TO WATCH

https://www.youtube.com/watch?v=Qesxa71v
fkM

https://www.youtube.com/watch?v=pmUhkQj
Hr3A
 TABLE SUMMARY

Particle Relative Relative Position

mass Charge within atom
Proton 1 +1 Nucleus

Neutron 1 0 Nucleus

Electron 1/1840 -1 In space

outside
nucleus
 ATOMIC NUMBER (Z)

• The number of protons in the nucleus

• An atom is neutral therefore the
number of protons is also equal to the
number of electrons
 MASS NUMBER (A)

• The number of protons

plus the number of
neutrons in an atom
 ISOTOPE

• Nuclide that has the same atomic number ( same

number of protons) but different mass number
( number of neutrons )

• Atom with a specified mass and proton number (

so basically your elements that you know the
mass and proton number for )
 RELATIVE ATOMIC MASS

• The mass of one atom of an element relative to the

mass of 1/12th the mass of carbon-12 (carbon 12 mass
actually =12) .

• The relative atomic mass is determined from the

average of the masses of the stable isotopes of the
element , weighed to take into account relative
abundance of each isotope .
 RELATIVE ABUNDANCE

• The proportion of each isotope that exists in a

sample of each element .
• Eg . Cl has two naturally occurring isotopes
• Cl-35 and Cl-37
• The abundance of Cl-35 is 78.5% meaning 78.5
percent of a sample of Cl will be Cl-35
 RELATIVE ISOTOPIC MASS

• Mass of a specific isotope relative to the mass of

1/12th the mass of carbon-12 (actually =12)
• To calculate relative mass from isotopic mass
and abundance
Sum of ((abundance of isotope 1 X isotopic mass)
+ (abundance of isotope 2 X isotopic mass))/100
PROBLEMS ON ISOTOPES
HOW IS RELATIVE ABUNDANCE
DETERMINED

• A mass spectrometer is used to compare the relative

masses
• The basic steps involved n the analysis are
• Vaporisation
• Ionisation
• Acceleration
• Deflection
• Detection
 VAPORISATION

• Gases , liquids and volatile

solids vaporise when injected
into the instrument just before
the ionization chamber .
 IONIZATION

• An electron gun is used to bombard

the sample by high energy electrons
that “knock” out the electrons from
the sample turning the atom into a
positive ion
 DETECTION

After passing through deflection only ions of

a particular mass will hit the detector and
these will be recorded. The ion detector will
be linked through an amplifier to a recorder
so the ions detected will be recorded.
 ACCELERATION

• Electric field is used to

accelerate the positive ion to
high speed.
 DEFLECTION

As the ions pass through a magnetic

field they are deflected based of their
relative mass ( strength of magnetic
field is increased over time )
INSERT VIDEO HERE
 RADIOACTIVITY

• When the number of protons in an atom increases

the like charges begin to repel each other and the
number of neutrons that is now needed to keep the
nucleus stable then increases , even more so than
the number of protons .
• Even with increasing the number of nuclei to keep
the nuclei stable atoms that have more than 84
protons tend to be unstable .
 RADIOACTIVITY

• The unstable nuclei is called a radioactive isotope .

• In order to become stable the atoms emit alpha
particles , beta particles and gamma radiation .
• This will change the number of protons in the
nucleus so that a different atom is produced.
• The types of particles emitted will depend on where
the atom stands on the band of stability .
BAND OF STABILITY
 CONT’D

 For stable isotopes,
an interesting plot arises when the
number of neutrons is plotted versus the number of
protons.
Because the plot shows only the stable isotopes,
this graph is often called the Nuclear Belt of Stability
or Band of stability.
 The plot indicates that lighter nuclides (isotopes) are
most stable when the neutron/proton ratio is 1/1. 
 CONT’D

• This is the case with any nucleus that has up to 20 protons.

•  As the atomic number increases beyond 20, a different
trend becomes apparent. In this range, it appears that a
stable nucleus is able to accommodate more
neutrons. Stable isotopes have a
higher neutron to proton ratio, rising to 1.5/1 for elements
having atomic numbers between 20 and 83.
 ALPHA DECAY

• During alpha decay, the mass number of the nuclide

decreases by 4 units and the number of protons
decreases by 2. 
• This type of decay is associated with heavy, unstable
nuclides. Since no stable isotopes exist above atomic
number 83, alpha decay stabilizes those isotopes
having a Z value greater than 83 by lowering both
the mass number and the atomic number. 
 CONT’D

• As an alpha particle is emitted, the number of

neutrons and protons decreases, creating a more
stable type of atom.
 BETA DECAY

• During beta emission, the net effect is that a neutron becomes

a proton (it disintegrates and forms a proton and an electron)
•  The overall mass of the nuclide remains constant, since a proton and
a neutron have approximately the same amount of mass. ability.
• The result of beta decay is that the number of neutrons goes down by
one while the number of protons goes up by one. 
• The neutron/proton ratio decreases, creating a more stable
nuclide. Thus, when the n/p ratio is high, beta decay is
favourable. This region corresponds to nuclides that would be
found above the band of stability.
 GAMMA RAYS

• Theses are electromagnetic waves of short wavelength. Emissions of

alpha and beta particles are often accompanied by the emission of
gamma rays.
• When particles are emitted the atomic nucleus becomes excited and
the excess energy is released as gamma radiation for the nucleus to
return to a more stable energy level.
• The penetrating power of alpha rays, beta rays, and gamma rays varies
greatly. Alpha particles can be blocked by a few pieces of paper. Beta
particles pass through paper but are stopped by aluminum foil.
Gamma rays are the most difficult to stop and require concrete, lead,
or other heavy shielding to block them
• Uses and disposal of radioisotopes –see pamphlet .
ENERGY LEVELS AND EMISSION
SPECTRA
• Electrons in an atom have fixed amounts of energy , the smallest
possible quantity of energy that an atom posses is called a quantum
• Electrons are arranged at different levels based on the energy that they
posses : energy levels
• At the lowest possible energy level ( smallest amount of energy ) the
electron is said to be in its ground state
• When electrons absorb energy ( example heat from a Bunsen flame or
from an electric discharge) they can go through a process called
excitation .
• During this process they are now in an excited state change energy
levels ( move to a higher energy level)
• When the electrons move to these higher energy levels they are not
stable and after a while will lose the energy they absorbed and fall
back to a lower energy level .
• When an electron moves from one energy level to another this is
called electronic transmission .
• The energy levels have fixed values so he amount of energy it loses
will be equal to the difference in the energy levels it moves between.
• An emission spectra shows evidence of this.
• The energy released from the electrons moving from an higher energy
level to a lower one is in the form of electromagnetic radiation.
• Electromagnetic radiation can be considered as a stream of photons
(particles with no mass) each travelling in a wave like pattern moving
at the speed of light . Electromagnetic radiation is energy that can
travel through a vacuum . Light is a form of electromagnetic radiation.
• Since electromagnetic radiation travels like waves : electromagnetic
radiations are characterized by their frequencies and wavelengths.
• The frequency and the wave length of electromagnetic radiation is related by :

c = νλ or ν = c/λ or λ = c/ν
ν= Frequency s-1 (Hz)
λ= Wavelength m or nm
C = speed of light ( 3x 108 ms-1)
• As energy is directly proportional to the frequency of the radiation , the change n energy from one level to
another can also be calculated using the following equation:

E=hν
Where E = energy
ν= frequency
h is Planks constant which is
( 6.63 x 10-34 Js)
• By using both equations the energy can also be calculated by
• E=hc/ν

• The whole range of frequencies of electromagnetic radiation is called

the electromagnetic spectrum. When energy is absorbed or emitted by
an element it will correspond to a specific point on this spectrum .
DIFFERENT SPECTRUMS
• Continuous spectrum -  a spectrum (as of light emitted by a white-hot
lamp filament) having no apparent breaks or gaps throughout its
wavelength range
• Emission spectrum -the spectrum formed by
 electromagnetic radiations emitted by a given
 source, characteristic of the source and the type of excitation including
radiations
The lines on an emission spectrum will have wavelengths that correspond
to the energy emitted when an excited electron transitions.
• Emission spectrum usually looks like a band of lines on a black
background
• All substances produce an emission spectrum when they are excited
whether by heat energy or electrical energy.

• The emission (and absorption) spectra of atoms give us an

understanding of the arrangement of electrons within the atom.

• Each atom has a unique emission or absorption spectra

ADSORPTION SPECTRUM
• As the energy levels have different values, each of the possible
electron transitions within an atom will produce a photon with a
different energy.
• This means that each electron transition will produce a photon of a
different frequency and hence a different colour.
• Because different types of atoms have different energy levels, the
photons produced will be different and so the line spectra for different
elements will be different. Line spectra can be used to identify
elements.
EMISSION SPECTRA OF
HYDROGEN
 THE BOHR MODEL OF THE
ATOM
• This model aimed to explain the observation that electromagnetic
radiation emitted by an excited atom has specific energies.
• Electrons are in circular orbits of fixed or quantized energy.
– They will not absorb or emit energy as long as they stay within this orbit.
• Therefore the energy of the electron in an atom must also be
quantized..i.e..an electron can only have certain discrete energy
levels.
• Each line on the hydrogen emission spectra therefore corresponds to a
drop from one specific energy level to another
• From the link of E=hν each quantum of energy will have a different
frequency therefore will represent a different line on the spectrum .
The lines are named depending on where on the spectrum they fall
 SHELLS AND SUBSHELLS

• Bohr labelled each of the energy levels with a number called the
principal quantum number, n.

• The energy level closest to the nucleus is labelled n=1, the next n=2 etc.

• Each of these energy levels is called a shell.

• The principal quantum number defines the energy level of the electron in
a given shell.
• The Bohr model of shells is one dimensional and accurately depicts
the quantum number of hydrogen but not the other elements with more
than one electron .
• When thinking about the position of the electron It is impossible to
determine both the position and the momentum of an electron in
an atom simultaneously with great certainty.
• This is know as The Heisenberg Uncertainty Principle
• Heisenberg showed an electron’s position can never be accurately be
determined.
• A wave function, however, tells where the electron will most
probably be found.
• Schrödinger Wave Equation. (assumes wave particle duality)
• This equation describes the electron in terms of probability
density ,the space in which the electron is likely to be found)
• The area the electron is located is called an orbital (spatial
distribution of electron density)
• Orbitals are defined by Quantum numbers: n, l, ml

Principal Quantum number – n

Angular quantum number – l
Magnetic quantum number – m
The principal quantum number describes the energy level of the electrons
where the maximum number of electrons for n = 2n2
N=1 has 2 , n=2 has 8, n=3 has 18 , etc
• Angular quantum number l, describes the sublevels in n and the shape
of the orbitals . The sublevels are given letter designations
• S, p, d, and f
• Each energy level has n sublevels .
• n = 1 has 1 sublevel (1s)
• n = 2 has 2 sublevels ( 2s , 2p)
• n = 3 has 3 sublevels ( 3s, 3p, 3d)
• n = 4 has 4 sublevels ( 4s, 4p, 4d, 4f)
• The magnetic quantum number m describes the number of orbital's
within a sublevel
• s has 1 orbital and can hold up to 2 electrons
• p has 3 orbitals and can hold up to 6 electrons
• d has 5 orbitals and can hold up to 10 electrons
• f has 7 orbitals and can hold up to 14 electrons
 SHAPES OF THE ORBITALS

S orbitals are spherical

There is only one possible orientation of a sphere: ml = 0

There is one s orbital per shell

The size on the orbital increases as you go to a higher shell

 P ORBITALS

• These are dumbbell-shaped.

• The electrons are distributed in identical lobes on either side of the nucleus.

• The lobes are separated by a nodal plane that cuts through the nucleus.

• When l = 1, ml has three possibilities, one along the x, y and z axes oriented at 900
angle to each other.

• As n increases, the size of the p orbital increases

 ELECTRON CONFIGURATIONS
(E.C.)
• Electron Configurations refers to the arrangement of electrons in an
atom

• Each atom has its own electronic configuration

• As the orbitals are at different energy levels there are 3 basic rules to
writing electron configurations.
1- PAULI EXCLUSION PRINCIPLE

• The Pauli Exclusion Principle states that, in an atom or molecule, no

two electrons can have the same four electronic quantum numbers. As
an orbital can contain a maximum of only two electrons, the two
electrons must have opposing spins
• Basically No more than 2 electrons can occupy an orbital
 2- AUFBAU PRINCIPLE

• The aufbau principle states that in the ground state of an atom or ion,

electrons fill atomic orbitals of the lowest available energy levels
before occupying higher levels. For example, the 1s shell is filled
before the 2s subshell is occupied
• Basically – electrons are added one at a time starting with the
orbital with the lowest energy.
 3- HUND'S RULE.

•  Hund's rule: every orbital in a subshell is singly occupied with one

electron before any one orbital is doubly occupied, and all electrons in
singly occupied orbitals have the same spin.
REPRESENTING ELECTRONIC
CONFIGURATION
 EXAMPLES

• N
• O
• F
• Ne
• Then representing spins
• For a one-electron hydrogen atom, orbitals on the same energy level
have the same energy.
• As the number of electrons increases, though, so does the repulsion
between them.
• Therefore, in many-electron atoms, orbitals on the same energy level
no longer have the exact same energy
ENERGIES OF ORBITALS

START HERE AND MOVE ALONG

THE ARROWS ONE AT A TIME
• Write the electronic configuration for the following elements and ions
• Sc
• Cr
• Cu
• Mg2+
• N3-
 IONIZATION ENERGIES

• Ionization energy is the energy required to turn one mole of an

element in its gaseous state to an ion with a single positive charge
( that is to remove one electron)
• This is the first ionization energy as one electron was removed .
• After the second electron it’s the second ionization energy , and so on
• Ionization energy is always positive as it will always require energy to
remove an electron .
• The value of the ionization energy will depend on the following :
• A- the distance of outer electrons from the nucleus
• B- The size of the positive nuclear charge
• C- the screening (shielding) effect of the inner shells of electrons.
THE DISTANCE OF THE OUTERMOST
ELECTRON FROM THE NUCLEUS

• As this distance increases, the attraction of the positive nucleus for the
negative electron decreases and consequently the ionization energy
decreases.
 THE SIZE OF THE POSITIVE
NUCLEAR CHARGE
• As the nuclear charge becomes more positive with increasing proton
number , its attraction for the outermost electron increases and
consequently the ionization energy increases .
• ( it should be noted that increasing atomic radii and shielding
outweighs the increasing nuclear charge . )
 THE SCREENING (SHIELDING)
EFFECT OF THE INNER SHELLS OF
ELECTRONS.
• Electrons in the inner shells exert a repelling effect on electrons in the
outermost shell of an atom, this is called screening /shielding .
• This screening effect means that the effective nuclear charge is much
less than the full positive charge in the nucleus .
The screening effect by the inner electrons is more effective the closer
these inner electrons are to the nucleus which means that :
Electrons in shells of lower principal quantum numbers are more effective
shields than those of higher quantum numbers
Electrons in the same shell have a negligible shielding effect on each
other.
 EVIDENCE OF ENERGY LEVELS
AND SUBSHELLS
• An element can have as much successive ionization energies as it has
electrons .
• The patterns in successive ionization energies for an element gives
important about the structure of the element .
 WHY ARE SUCCESSIVE IONISATION
ENERGIES ALWAYS LARGER?

• The second ionisation energy of an element is always bigger than the

first ionisation energy. When the first electron is removed a positive
ion is formed. The ion increases the attraction on the remaining
electrons and so the energy required to remove the next electron is
larger.
• Each successive ionisation energy is bigger than the previous one for
the same reason. Some of the increases are much bigger, however, and
these big jumps gives us evidence for the main principle electron
shells.
• Example: What group must this element be in?

1 2 3 4 5
Ionisation 590 1150 4940 6480 8120
energy kJ
mol-1
• there is a big jump between the 2nd and 3rd ionisations energies which
means that this element must be in group 2 of the periodic table as the
3rd electron is removed from an electron shell closer to the nucleus
with less shielding and so has a larger ionisation energy
• The pattern in the first ionisation energy of each successive element in
the periodic table also gives us useful information about electronic
structure.
• The noble gases are always at the maximum peak for each period, but
there is a decrease in ionisation energy down the group. (true of all
groups). This is because as one goes down the group the outer
electrons become further from the nucleus and become more shielded
from the nuclear pull by complete inner shells
• There is a large drop each time between the group 0 elements and the
group1 elements. This is because the element in group 1 will have its
outer electron in a new shell further from the nucleus and is more
shielded. So the group 1 element is easier to remove and has a lower
ionisation energy
From the graphs of successive ionisation energies below, explain which
group of the periodic table the elements belong to.
• 2) Study the graph of 4th to 11th ionisation energies for aluminium.
• a) Explain why there is a large increase in ionisation energy between
the 9th and 10th ionisation energies.
• b) Explain why the increase between the 6th and 7th ionisation
energies is greater than the increase between the 5th and 6th ionisation
energies.