Atomic Structure and

Periodic Table
IAS CHEMISTRY
UNIT 1

Ms. Pabasari Goonetilleke

A bit from the History
Francis William Aston invented the mass spectrometer which accurately
measured the mass of atoms
nucleus
Behavior of beams of protons, neutrons and electrons in electric fields

• The negatively charged electron is

attracted towards the positive plate

• The neutron has no charge and is

unaffected by a charged field

• The positively charged proton is attracted

towards the negative plate.

• It is deflected less than an electron as it

has a larger mass
Mass Number and Atomic Number

Proton (Atomic number) – Z : The number of protons in the nucleus

Mass (Nucleon number) – A : The total number of protons and neutrons in the atom

Number of neutrons = A – Z
 Isotopes
• Isotopes are atoms with the same number of
protons, but different numbers of neutrons

• Isotopes are atoms with the same atomic

number, but different mass numbers

• Isotopes have similar chemical properties

because they have the same electronic
structure

• They may have slightly varying physical

properties because they have different
masses
Uses of isotopes

• Medical uses – In cancer treatment

(Co is used), treatment of overactive
thyroid glands, locating tumors in the
body and to sterilize medical
equipment
• Industrial uses- to check for leaks in oil
and gas pipelines, to control thickness
in paper and in smoke detectors
• Military purposes
• Mass Spectrometry is a process by which the atomic mass of atoms or molecules
is determined

• It can be used to find

• relative isotopic abundance
• atomic and molecular mass
• structure of a compound

• The result of a Mass Spectrometry is a graph plotting mass per

charge against relative abundance
• Mass spectrometers have been included in planetary space probes so that
elements on other planets can be identified. Elements on other planets can
have a different composition of isotopes
• Drug testing in sport to identify chemicals in the blood and to identify
breakdown products from drugs in body
• Quality control in pharmaceutical industry and to identify molecules from
sample with potential biological activity
• Radioactive dating to determine age of fossils or human remains
Other uses of Mass spectrometers
 Instrumentation

Watch: https://www.youtube.com/watch?v=J-wao0O0_qM&t=3s
There are four essential steps in a mass spectrometer

1. Ionization
2. Acceleration
3. Deflection
4. Detection
The need for a vacuum
• The ions produced in the ionization chamber have a free run through the machine
without hitting air molecules
• Otherwise air particles would ionized and register on the detector
1. Ionisation

• A Vaporised sample is injected at low pressure

• An electron gun fires high energy electrons at the sample
• This Knocks out an (outer) electron forming positive ions with different charges

Eg: Ti (g) Ti+ (g) + e–

• If the sample is not vaporized then vaporizing it would be the first step
2. Acceleration

• A negative electric field accelerates the positive ions and makes them into a
beam
3. Deflection

• The beam of positive ions is deflected by a strong magnetic field

• The degree of deflection depends on the mass-to-charge ratio, m/z
• The mass of the ion - Lighter ions are deflected more than heavier ones
• The charge on the ion - Ions with 2 (or more) positive charges is deflected
more than ones with only +1 charge

• The smaller this ratio the larger the deflection

• By varying the magnetic field ratio, ions of different m/z ratios pass through the
centre
• Ion stream A is most deflected - it will contain ions with the smallest mass/charge ratio
• Ion stream C is the least deflected - it contains ions with the greatest mass/charge ratio
• Only ion stream B makes it right through the machine to the ion detector
• The other ions collide with the walls where they will pick up electrons and be
neutralized

• Eventually, they get removed from the mass spectrometer by the vacuum pump

• To bring streams with small m/z value (eg: Stream A) on to the detector, you
would need to deflect them less - by using a smaller magnetic field (a smaller
sideways force)

• To bring those with a larger m/z value (the heavier ions if the charge is +1) on to
the detector you would have to deflect them more by using a larger magnetic
field
4. Detection

• The ions reach the detector and generate a small current, which is fed to a
computer for analysis
• The current is produced by electrons transferring from the detector to the
positive ions
• The size of the current is proportional to the abundance of the species
Molecular ion (M+)

• Vaporised sample is bombarded with electrons in the ionization chamber

• These electrons have a high enough energy to knock an electron off an organic molecule
to form a positive ion which is called the molecular ion

• The molecular ion is often given the symbol M+ or M

.

• The dot in this second version represents the fact that somewhere in the ion there will be
a single unpaired electron. That's one half of what was originally a pair of electrons - the
other half is the electron which was removed in the ionisation process
Molecular ion (M+)
• The molecular ions tend to be unstable and some of them break into smaller
fragments

• These fragments produce the familiar stick diagrams

• The heaviest ion (the one with the greatest m/z value) is likely to be the molecular
ion

• A few compounds have mass spectra which don't contain a molecular ion peak,
because all the molecular ions break into fragments
Eg: Mass spectrum of pentane

• The heaviest ion has an m/z value of 72

• This is the molecular ion
• The relative formula mass of the compound is therefore 72
Eg: Mass spectrum of pentane

• The heaviest ion has an m/z value of 72

• This is the molecular ion
• The relative formula mass of the compound is therefore 72
 M+1 peak
• The small line to the right of the main molecular ion peak is called the M+1 peak

The M+1 peak is caused by the presence of the 13C isotope in the molecule
The line at M+1 will be much smaller than the line at M+ because the carbon-13
isotope is much less common
Using a mass spectrum to find a molecular formula

Eg: A gas was known to contain only elements from the following list:
1H 1.0078
12C 12.0000
14N 14.0031
16O 15.9949
The gas had a molecular ion peak at m/z = 28.0312 in a high resolution mass spectrometer. What was the gas?

Possible gases are N2, CO and C2H4

Working out their accurate relative formula masses gives:
N2 28.0062
CO 27.9949
C2H4 28.0312 The gas is C2H4
The mass spectrum for boron

• The relative sizes of the peaks give you a direct measure of the relative abundances of the isotopes
boron-10 23
boron-11 100
• Work out the relative atomic mass
RAM = (23 x 10) + (100 x 11)
123
= 10.8 (to 3 significant figures)
The mass spectrum for zirconium

Use the data given below to calculate the RAM

of Zr

• zirconium-90 51.5
• zirconium-91 11.2
• zirconium-92 17.1
• zirconium-94 17.4
• zirconium-96 2.8
The mass spectrum of chlorine

• When chlorine is passed into the ionisation chamber, an electron is knocked off the
molecule to give a molecular ion, Cl2+
• These ions won't be particularly stable, and some will fall apart to give a chlorine
atom and a Cl+ ion
• The term for this is fragmentation

• The result of the ionisation process and subsequent fragmentation of chlorine

molecules is a series of 5 different mass peaks
• [37Cl 37Cl]+ or [37Cl2]+ m/z = 74 (molecular ion)
• [37Cl 35Cl]+ m/z = 72 (note that you must show the two isotopes separately in the molecular ion)
• [35Cl 35Cl] + or [35Cl2] + m/z = 70 (molecular ion)
• [37Cl]+ m/z = 37 (mononuclear ion, monatomic fragment)
• [35Cl]+ m/z =35 (mononuclear ion, monatomic fragment)
Electronic structure

• Electrons in an atom are grouped around the nucleus into shells according to the
energy
• The energy of an electron shells increase when going away from the nucleus
• The difference in energy between energy levels will decrease with increasing
energy levels
Niels Bohr and Quantum Shells
Emission Spectra
Energy transfer in Hydrogen
The hydrogen electron is found in the first quantum shell but can be excited to higher
energy levels. The arrows represent the electron returning back to lower energy levels
 Main Energy Levels
• The path of the electrons are referred to as
Main Energy Levels denoted by K, L, M, N, …
(n = 1, 2, 3, 4)

• Electrons are filled from the lowest energy

level which is the 1st energy level

• The energy of an electron shells increase

when going away from the nucleus and the
difference in energy between energy levels
will decrease with increasing energy levels
• Electrons are filled from the lowest energy
level which is the 1st energy level
Sub energy levels

• There are sub energy levels in each energy level

• Each subshell has different number of orbitals depending on their shape (s, p, d, f)
• Energy of the subshell increases as s < p < d < f
 Orbitals

• Orbitals are negatively charged clouds around the nucleus where the probability of
finding an electron is high
• Any orbital can hold a maximum of 2 electrons with opposite spin
• Number of orbitals for each energy level can be found using, n2

Main energy level Orbitals

(n) (n2)
1 1
2 4
3 9
4 16
S (1)
S (1) + p (3)
S (1) + p (3) + d (5)
S (1) + p (3) + d (5) + f(7)
Shapes of orbitals

s orbital p orbitals

Spherical shape Dumbbell shape

They are perpendicular to each other
d orbitals

f orbitals
 Number of Number of
Main Shell Sub Shell
orbitals electrons
1K 1s 1 2
2s 1 2
2L
2p 3 6
3s 1 2
3M 3p 3 6
3d 5 10
4s 1 2
4p 3 6
4N
4d 5 10
4f 7 14
 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

Eg: 1s shell is filled before the 2s subshell is

occupied
Pauli’s Exclusion Principle
• An orbital can contain a maximum of only two electrons
• The two electrons must have opposing spins

• This means if one is assigned an up-spin ( +1/2) - clockwise, the other must be
down-spin (-1/2) – anti clockwise ( This neutralize the repulsion between the
negative charges)
Hund’s Rule
• Electrons organize themselves so that as far as possible they remain unpaired,
occupying the maximum number of degenerate orbitals possible
First ionisation energy

The first ionisation energy is the energy required when one mole of gaseous atoms
forms one mole of gaseous ions with a single positive charge (+1) – unipositive under
standard conditions

Eg: H (g) → H+ (g) + e-

Be (g) → Be+ (g) + e-
O (g) → O+ (g) + e-
Second ionisation energy

The second ionisation energy is the energy required when one mole of gaseous
ions with a single positive charge (+1) forms one mole of gaseous ions with a
double positive charge (+2) – dipositive under standard conditions

Eg: Ti + (g) → Ti 2+ (g) + e-

Third ionisation energy

• The third ionisation energy is the energy required when one mole of gaseous ions
with a double positive charge (+2) forms one mole of gaseous ions with a +3
charge under standard conditions

Eg: Al 2+ (g) → Al 3+ (g) + e-

 Factors that affect Ionisation energy

• Atomic radius
• Nuclear charge
• Electron shielding/ screening effect
1. Atomic radius
• Refers to the distance between the nucleus and outer shell
electron

• The nuclear attraction on the outer shell electron

decreases when the atomic radius increases
• So the amount of energy needed to remove the outer
shell electron, that is the ionisation energy deceases
2. Nuclear charge

• Refers to the number of protons in the nucleus of an atom

• The nuclear attraction on the outer shell electron increases when the nuclear charge
increases
• So the amount of energy needed to remove the outer shell electron, that is the
ionisation energy increases

• The effective nuclear charge is the actual amount of

positive (nuclear) charge experienced by an electron in a
multi-electron atom.
• The term "effective" is used because the shielding
effect of negatively charged electrons prevent higher
energy electrons from experiencing the full nuclear
charge of the nucleus due to the repelling effect of inner
layer.
3. Electron shielding/ screening effect

• Refers to the number of filled electron shells between the

nucleus and outermost shell

• The nuclear attraction on the outer shell electron

decreases when the shielding effect increases
• So the amount of energy needed to remove the outer
shell electron, that is the ionisation energy decreases
Successive Ionization energies

Trend in successive ionization energies can be seen when the logarithm of

ionization energy is plotted against the order of electron removal
Successive Ionization energies
 Successive Ionisation energies

• Successive ionisation energy for an element would increase because when every
electron is removed the nuclear attraction on the next electron to be removed
would be larger

• The graph of successive ionisation energy against number of electrons removed

would give the following information:

• Electronic configuration of the element

• Existence of electrons in different energy levels
• The group of the element
Sodium has one valence electron
– It should b e in group 1

Sodium has 11 electrons

– Electronic configuration is,
Trends in ionisation energies
• Helium has the biggest first ionisation energy because its first electron is in the
first shell closest to the nucleus and has no shielding effects from inner shells.
• Helium has a bigger first ionisation energy than hydrogen as it has one more
proton
• The large drop between the group 0 elements and the group1 elements 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
• Noble gases have the highest ionisation energy in a period. They have the highest
nuclear charge for a given period so the nuclear attraction on the outer shell
electron is stronger since the electron must be removed from a completely filled
outer shell
Ionisation Energy down the group
Down a group,

- The nuclear charge increases as the number of protons increases

- Thus, the nuclear attraction on the outer shell electron increases so ionisation
energy increases
- One new quantum shell is added so the atomic radius increase and the electron
shielding effect increase
- Thus, the nuclear attraction on the outer shell electron decreases so ionisation
energy decreases
- The combined effect of adding an extra shell and increasing the shielding is more
significant than increase in nuclear charge
- So ionisation energy decreases down the group
Ionisation Energy across the period

Period 3

Period 2
Across a period

- The nuclear charge increases as the number of protons increases

- Thus the nuclear attraction on the outer shell electron increases so ionisation
energy increases
- Atomic radius slightly decreases so the electrons are pulled in closer to the
nucleus
- But the electrons are added to the same quantum shell so the electron shielding
effect remain the same
- So ionisation energy increases across a period
Evidence for main energy levels

• There is a big jump between the 4th

and 5th ionisation energies
• The 5th electron is in an inner main
shell closer to the nucleus and therefore
attracted much more strongly by the
nucleus than the 4th electron
• It also does not have any shielding by
inner complete shells of electron so is
easier to remove.
Evidence for sub energy levels

• There is a small drop between the group

2 elements and group 3 elements (Be - B
, Mg - Al)
• Aluminium is starting to fill a 3p sub
shell, whereas magnesium has its outer
electrons in the 3s sub shell
• The electrons in the 3p subshell are
slightly easier to remove because the 3p
electron sub shell is slightly higher in
energy and they are also slightly
shielded by the 3s electrons.
• small drop from phosphorous to sulfur (Group 5 and group 6)

• In sulfur, there are 4 electrons in the 3p sub shell and the 4th is starting to doubly fill
the first 3p orbital
• When the second electron is added to a 3p orbital there is a slight repulsion between
the two negatively charged electrons which makes the second electron easier to
remove
 • The periodic table is the
arrangement of elements in the
increasing atomic number
• Grouped according to the
reactivities based on electronic
configuration
• Vertical columns are called Groups
• Horizontal rows are called Periods

• Elements in the same group has same number of electrons in the outer shell
• Electrons are added to the same main energy level in elements of the same period
• The number of the principal energy level and the number of the valence electrons
in an atom can be deduced from its position on the periodic table
The periodic table is split into blocks
- An s block element is one whose outer electron is filling a s-sub shell
• Eg: sodium 1s2 2s2 2p6 3s 1
- s block elements have low melting and boiling points and are referred as soft metals

- A p block element is one whose outer electron is filling a p-sub shell

• Eg: chlorine 1s2 2s2 2p6 3s2 3p5
- p block includes less reactive metals, metalloids(semi metals- B, Si, Ge, As, Sb, Te) and
non metals

- A d block element is one whose outer electron is filling a d-sub shell

• Eg: vanadium 1s22s22p63s23p6 4s23d3
- They are called transition metals which are comparatively less reactive but have high
melting and boiling points and considered strong metals
- They form colored compounds

- f block elements are usually synthetic and radioactive

Lanthanides and Actinides
• We see some hidden "layers" in chemistry.
• Examining the periodic table below, visible
are two pink boxes—one between Ba
(element 56) and Hf (element 72) and the
other between Ra (88) and Rf (104).
These elements all have unfilled f -
sublevels.
• Because of the uniqueness of the electron
configurations, these elements fit into the
two boxes in the larger periodic table.
• Due to the way the electron energy levels
work, some inner levels fill after one or
more outer layers do. We see this in two
similar groups of elements—the lanthanides
and the actinides.
 Periodicity

• The periodic table shows trends

of chemical and physical
properties.

• The repeating trends are called

Periodicity
Atomic radius
Across the period

• Atomic radii decrease from left to right across

a period
• The increased number of protons create
more positive charge attraction for electrons
which are in the same shell with similar
shielding since the electrons are added to the
same energy level
• The radius shows a slight increase from group
7 to group 8 since group 8 has a completely
filled outer shell which results in maximum
mutual repulsion

• Exactly the same trend in period 2

Down a group

• Atomic radii increase down the group

• Irrespective of increase of nuclear charge,

the number of energy levels increases as
you move down a group and the electron
shielding effect would increase
First ionization energies
Across a period

• IE increases

• This is due to increasing number of protons as the electrons are being added to the
same shell

• There is a small drop between Mg - Al. Mg has its outer electrons in the 3s sub shell,
whereas Al is starting to fill the 3p subshell. Al’s electron is slightly easier to remove
because the 3p electrons are higher in energy

• There is a small drop between P - S. Sulphur’s outer electron is being paired up with
another electron in the same 3p orbital. When the second electron is added to an
orbital there is a slight repulsion between the two negatively charged electrons
which makes the second electron easier to remove
Down a group

• IE decreases
• The nuclear charge increases as the number of protons increases
• Thus, the nuclear attraction on the outer shell electron increases so ionization
energy increases
• One new quantum shell is added so the atomic radius increase and the electron
shielding effect increase
• Thus, the nuclear attraction on the outer shell electron decreases so ionization
energy decreases
• The combined effect of adding an extra shell and increasing the shielding is more
significant than increase in nuclear charge
Melting and boiling points
• Mp and bp of elements depends on the bonds between atoms and the
intermolecular forces
• Simple molecules have very weak intermolecular forces between
molecules which makes mp low
• Metals have metallic bonds to be broken when melted.
Na, Mg, Al

• The strength of the metallic bonds depends on delocalized electrons

• Bonding gets stronger the more electrons there are in the outer shell that are
released to the sea of electrons.
• A smaller positive center also makes the bonding stronger.
• High energy is needed to break bonds.
Si

Macromolecular structure
Many strong covalent bonds between
atoms high energy needed to break
covalent bonds– very high mp and bp
 Cl, S, P. Ar

• Simple Molecular structures

• Exist as Cl2 (g), S8 (s), P4 (S), Ar (g)
• Weak London forces between molecules, so little energy
is needed to break them – low mp and bp
• S8 has a higher mp than P4 because it has more electrons
(S8 =128)(P4 =60) so has stronger London forces.
• P4 has a higher mp than Cl2 because it has more electrons
(P4 =60) (Cl2 =34) so has stronger London forces.
• Ar is monoatomic - weak London Forces between atoms
Questions??
Thank you