ATOMIC STRUCTURE

1. Particles in atoms and atomic radius

2. Isotopes
3. Electrons, energy levels and atomic orbitals
4. Ionisation energy
 Structure of an Atom
• All matter is composed of atoms,
smallest parts of an element that can take place
in chemical reactions
• Atoms are mostly made up
of empty space around a very small,
dense nucleus that
contains protons and neutrons
• Subatomic Particles
• Protons
• Electrons
• Neutrons
• Protons and neutrons are also called nucleons,
because they are found in the nucleus
 Subatomic Particle
• These subatomic particles are so small that it is not possible to measure their masses
and charges using conventional units

• Instead, their masses and charges are compared to each other

• relative atomic masses
• relative atomic charges

• Protons and neutrons have a very similar mass, so each is assigned a relative mass
of 1

• Electrons are 1836 times smaller than a proton and neutron, and so their mass
is often described as being negligible Position
Subatomic Symbol Relative Relative within the
Particle Mass Charge atom
Electron e 1/1836 -1 Shell
Neutron n 1 0 Nucleus
Proton p 1 +1 Nucleus
• Electrons orbit the nucleus of the atom, contributing very little to its
overall mass, but creating a ‘cloud’ of negative charge
• The electrostatic attraction between the positive
nucleus and negatively charged electrons orbiting around it is what
holds an atom together
 The behaviour of beams of subatomic
particles in an electric field
• Protons, neutrons and electrons behave differently when they
move in an electric field

• A beam of electrons are deflected away from the negative plate

and towards the positive plate
• electrons are negatively charged
• opposite charges attract each other and like charges repel
each other.

• A beam of protons is deflected away from the positive plate and

towards the negative plate
 This proves that the proton is positively charged
 As protons are deflected less than electrons
 protons are heavier than electrons

• A beam of neutrons is not deflected at all

 neutral ; it is not attracted to, or repelled by,
the negative or positive plate
 Proton Number(Atomic Number) & Nucleon
Number (Mass Number)
• Proton Number/ Atomic Number, (Z)
• Number of protons in the nucleus of an atom
• Eg: atomic number of 11  Sodium, Na

• Nucleon Number/ Mass Number, (A)

• Total number of protons and neutrons in the nucleus of an atom

• The number of neutrons can be calculated by:

• Number of neutrons = mass number - atomic number
 How many neutrons?

• Deduce the number of electrons & neutrons in an atom

Proton Nucleon
Element Symbol Number Number No of protons No of electrons No of neutrons

Vanadium V 23 51 23 23 28

Strontium Sr 38 88

Phosphorus P

Calcium Ca 40

Bromine 80

Magnesium 24
 How to calculate number of
electrons in ions?
• An atom is neutral and has no overall charge
• Number of positively charged protons = Number of negatively charged electrons

• Ions: Charged particles formed by the loss or gain of electrons

• Positive ions (cation) are formed when one or more electrons are lost by an atom
• Negative ions (anion) are formed when one or more electrons are gained by an
atom
 How to calculate number of
electron in ions?
Ex: Chlorine atom gains electron

• Ex: Magnesium atom loses electron

12 electrons
 Question
Which of the sets of numbers in the table cannot be used to calculate
the numbers of subatomic particles in a neutral atom?
First number Second number
A proton number nucleon number
B proton number number of protons
C nucleon number number of neutrons
D number of electrons nucleon number
 Isotope
• Atoms of the same element that have same proton number (atomic number), but
different nucleon number (mass number) are called isotopes
• Isotopes have same proton number because they have same number of protons
• Isotopes have different nucleon number because they have different number of
neutrons
• The name of an isotope is the chemical symbol (or word) followed by
a dash and then the mass number

• For example, Chlorine isotope

 Chlorine-35 (Cl-35) have 17 protons & 18 neutrons
 Chlorine-37 (Cl-37) have 17 protons & 20 neutrons
 Same proton number but different nucleon number

• Chlorine isotopes: &

• Isotopes have same chemical properties
 Because they have same number of electrons
 Chemical properties depend upon the transfer and redistribution of electrons

• Isotopes have different physical properties

 Because they have different number of neutrons
 Physical properties such as density and mass
 For example: Chlorine-37 will have higher density than chlorine-35
 Question

140
58 Ce 3+ 𝑐𝐸
Question
Question 1

Question 2

Question 3
Question 4

Question 5

Question 6
 Simple Electronic Structure
• Electrons are arranged outside the nucleus in energy levels or quantum shells

• Principal energy levels or principal quantum shells (n)

 Numbered according how far they are from the nucleus
 Lowest energy level, n = 1, is closest to the nucleus
 n = 2 is further out and so on

• Electrons in quantum shells further away from the nucleus have more energy and are held less
tightly to the nucleus.
• Arrangement of electrons in an atom is called as electronic structure or electronic configuration

• Each principal quantum shell can hold a maximum number of electrons:

 shell 1: up to 2 electrons
 shell 2: up to 8 electrons
 shell 3: up to 18 electrons
 shell 4: up to 32 electrons
 Sub-shells
• The principal quantum shells are
split into sub-shells which are
given the letters s, p and d
• The energy of the electrons in the
sub-shells increases in the order s
<p<d

• The order of sub-shells appear to

overlap for the higher principal
quantum shells
 Atomic orbitals
• Each sub-shell contains one or more atomic orbitals

• An atomic orbital is a region of space around the nucleus of an atom

that can be occupied by one or two electrons

• As each orbital can only hold a maximum of two electrons, the

number of orbitals in each sub-shell must be:
 Shapes of the orbitals
• Each orbital has a three-dimensional shape

• s orbital
 Has a spherical shape

• p orbital
• The shape is like an hourglass with two ‘lobes’
• Three sets of ‘lobes’ are arranged at right angles to each other
along the x, y and z axes
• For example: 2px , 2py and 2pz
 Filling the Orbitals
• A useful way of representing electronic configurations is a diagram that places
electrons in boxes
 Each box represents an atomic orbital.
 The boxes (orbitals) can be arranged in order of increasing energy from bottom to top.
 An electron is represented by an arrow.
The direction of the arrow represents the ‘spin’ of the electron.
When there are two electrons in an orbital, the ‘spins’ of the electrons are opposite, so
the two arrows in this box point in opposite directions
 Spin-pair repulsion
• Electrons in the same region of space repel each other because they have the same charge
• Wherever possible, electrons will occupy separate orbitals in the same sub-shell to minimise
this repulsion. These electrons have their ‘spin’ in the same direction
• Electrons are only paired when there are no more empty orbitals available within a sub-shell
• The spins are then opposite to minimise repulsion
 How does electron fill the shells
& orbitals
• The ground state is the most stable electronic configuration of an atom which has the
lowest amount of energy
• Electrons always occupy lowest available energy sub-shell first to obtain most stable
electronic configuration
• The lowest energy level, the 1s is therefore filled first
• The order of the sub-shells in terms of increasing energy does not follow a regular pattern
of s then p then d after argon (where the 3p sub-shell is full)
 Electronic Configuration
• Electrons are added one by one for successive elements, filling each sub-shell in order of increasing energy
• Electronic configuration of an atom of hydrogen

• Examples of electronic configuration

a) He (2 electrons) : 1s2
b) Beryllium (4 electrons) : 1s2 2s2
Fill up the electronic configuration for the elements listed in the table.
• Energy level of sub-shell is 1s < 2s < 2p < 3s < 3p
• Electrons will occupy lower energy level first
• s orbital: 2 electrons, p orbital: 6 electrons

Element No of Electron Configuration Element No of Electron Configuration

electrons electrons
H 1 Ne 10
He 2 Na 11 1s22s22p63s1
Li 3 Mg 12
Be 4
Al 13
B 5 1s 2s 2p
2 2 1
Si 14
C 6
P 15
N 7
S 16
O 8
F 9 Cl 17
Ar 18
• The order of the sub-shells in terms of increasing energy does not follow a regular pattern
of s then p then d after argon
• After Argon, the pattern will be 1s<2s<2p<3s<3p<4s<3d<4p
• Electron goes into the 4s subshell rather than the 3d sub-shell because the 4s is below the
3d in terms of its energy

• For example:
a) Potassium ( 19 electrons) : 1s22s22p63s23p64s1 or [Ar]4s1
b) Calcium (20 electrons) : 1s22s22p63s23p64s2 or [Ar]4s2
c) Scandium (21 electrons) : 1s22s22p63s23p63d14s2 or [Ar]3d14s2

Full electronic Shorthand

configuration electronic
configuration
 Chromium & Copper

• Two exception cases : Copper (Cu) and Chromium (Cr)

• Chromium and copper do not follow the expected pattern

• Cr: [Ar]3d54s1 (rather than the expected [Ar] 3d44s2)

• Cu: [Ar]3d104s1 (rather than the expected [Ar] 3d94s2 )

• This is because the 3d54s1 and 3d104s1 electron arrangements are more
energetically stable
Element No of Electron Configuration
electrons
Potassium (K) 19
Calcium (Ca) 20
Scandium (Sc) 21
Chromium 24
(Cr)
Manganese 25
(Mn)
Copper (Cu) 29
Zinc (Zn) 30
Gallium (Ga) 31
Bromine (Br) 35
Krypton (Kr) 36
 Electronic configuration of ions
• Positive ions are formed when electrons are removed from atoms.
• The sodium ion, Na+ (proton number = 11), has 10 electrons
• 1s22s22p6

• Negative ions are formed when atoms gain electrons

• The sulfide ion, S2− (proton number = 16), has 18 electrons.
• 1s22s22p63s23p6

• In general, electrons in the outer sub-shell are removed when metal ions form their positive ions

• However, the d-block elements behave slightly differently

• Reading across the Periodic Table from potassium to zinc, the 4s sub-shell fills before the 3d sub-shell

• But when atoms of a d-block element lose electrons to form ions, the 4s electrons are lost first
• Ti atom: 1s22s22p63s23p63d24s2 → Ti2+ ion: 1s22s22p63s23p63d2
• Cr atom: 1s22s22p63s23p63d54s1 → Cr3+ ion: 1s22s22p63s23p63d3
• Use 1s2 notation to deduce the electronic configuration of an Fe3+ ion.
6
 Free radicals
• A free radical is a species with one or more unpaired electrons
• Example: An isolated chlorine atom, which has the electronic configuration
1s22s22p63s23p5
In the 3p orbitals, two of the orbitals have paired electrons and the remaining
orbital has an unpaired electron

• The unpaired electron in a free radical is shown as a dot ·

Cl·
• Groups of atoms can also be free radicals
• For example, the H3C· radical has a carbon atom with an unpaired electron
 Atomic Radius
• The atomic radius of an element is a measure of the size of an atom
• It is half the distance between the two nuclei of two covalently bonded
atoms of the same type

• Atomic radii show predictable patterns across the Periodic Table

• They generally decrease across each Period
• They generally increase down each Group
 Periodic pattern of atomic
radius
Atomic radius (Going DOWN the GROUP)
 Increases down any group
 Going down the group, each successive element has one more shell of electrons
 Although there is also an increasing nuclear charge going down the group, the increased effect
of inner shell electrons shielding the outer shell electrons is more important

Atomic radius (Going ACROSS the PERIOD)

 Decreases across any period
 This is because the number of protons and nuclear charge increases
 The number of electrons also increases by one but the extra electron added goes into the same
(outer) energy level.
 This means that the shielding does not change significantly.
 The greater attractive force of the increased nuclear charge on the outer shell electrons pulls
them closer to the nucleus.
 Shielding Effect
• As all electrons are negatively charged, they repel
each other

• Electrons in full inner shells repel electrons in outer

shells.
• preventing the outer electrons feeling the full
nuclear charge.
• This is called shielding

• The greater the shielding of outer electrons by the

inner electron shells, the weaker the attractive
forces between the nucleus and the outer electrons
 Ionic Radius
• The ionic radius of an element is a measure of the size of an ion
• Ionic radii increase with increasing negative charge
• Negatively charged ions are formed by accepting extra electrons while the nuclear charge remains the same
• The outermost electrons are further away from the positively charged nucleus and are therefore held
only weakly to the nucleus which increases the ionic radius
• The greater the negative charge, the larger the ionic radius

•Ionic radii decrease with increasing positive charge

• Positively charged ions are formed by atoms losing electrons
• The nuclear charge remains the same but there are now fewer electrons which undergo a greater
electrostatic force of attraction to the nucleus
• The greater the positive charger, the smaller the ionic radius
 Periodic pattern of ionic radius
• Ionic radius (Going ACROSS the PERIOD from Group 1 to Group 14)
 Decreases across any period
 The increasing nuclear charge attracts the electrons in the outer electron shell closer to the
nucleus with increasing atomic number
 The shielding is approximately the same, so has less effect than the increase in nuclear charge.

• Ionic radius (Going ACROSS the PERIOD from Group 15 to Group 18)
 From Group 15 to Group 18, the ionic radius decreases. This is for similar reasons to those for
decreasing atomic radii across a period

• Comparison of ionic and atomic radius

 Positively charged ions are smaller than their original atoms because they have lost their outer shell electrons.
 Negatively charged ions are larger than their original atoms because each atom will have gained one or more extra
electrons into their outer energy level.
 Periodic pattern of ionic radius
Ionic radius (Going DOWN the GROUP)
Increases down any group
In each group the number of electrons lost or gained by each element in
the group is generally the same.
For example, Group 2 elements form +2 ions and atoms of Group 17
elements form ions with a charge of − 1
The reason for the increase in ionic radius is similar to that for the
atoms.
Going down the group, each successive element has one more shell of
electrons which is further from the nucleus.
 Ionisation Energy
• The arrangement of electrons in atom can be obtained by studying the ease with which atoms lose
electrons

• Scientist fire high speed electrons at atoms to study how much energy is required to form an ion by
knocking out one electron from each atom

• The Ionisation Energy (IE) of an element is the amount of energy required to remove one mole of
electrons from one mole of gaseous atoms of an element to form one mole of gaseous ions

• The first ionisation energy of an element is the energy needed to remove one electron from each atom
in one mole of atoms of the element in the gaseous state to form one mole of gaseous 1+ ions

• Symbol: IE and SI unit: kJ mol-1

 Using IE to predict electronic
structures
• Additional supply of energy can result in removal of second, third, fourth and so on
• Sequence of ionisation energies is called successive ionisation energies
• Using sodium as an example
 Na (g)  Na+ (g) + e- IE1 = +494 kJ mol-1 First ionisation energy
 Na+ (g)  Na2+ (g) + e- IE2 = +4564 kJ mol-1 Second ionisation energy

• When you write equations for successive ionisation energies, remember that:
 the atoms and ions are in the gaseous state
 the charge on the ion on the right-hand side gives the number of the ionisation energy (1st, 2nd, 3rd,
etc.)
• Electrons can be removed from an atom until only the nucleus is left
• Using calcium as example
 Ca (g)  Ca+ (g) + e- IE1 = +590 kJ mol-1 First ionisation energy
 Ca+ (g)  Ca2+ (g) + e IE2 = +1150 kJ mol-1 Second ionisation energy
 Ca2+ (g)  Ca3+ (g) + e IE3 = +4950 kJ mol-1 Third ionisation energy

• Why does the successive IE increases?

• Net positive charge on the ion gets greater as each electron is removed
• As each electron is removed there is a greater attractive force between the
positively charged protons in the nucleus and the remaining negatively
charged electrons
• More energy is needed to overcome these attractive forces

• Why is there a big difference between some successive IE? For e.g. between
the IE1 and IE2 of Na
• Large changes indicate that for the second of these two ionisation energies
the electron is being removed from a principal quantum shell closer to the
nucleus
 The table below shows successive IE of beryllium. Twice as much energy needed to remove the second electron
from beryllium as to remove the first. However, eight times as much energy needed to remove the third electron
as the second. Why?

 Beryllium has 2 electrons which are relatively easy to remove and two electrons which are difficult to remove
 This suggest that beryllium has 2 electrons in low energy level (n=1) therefore very difficult to remove; and 2
electrons in a higher energy level (n=2), therefore easy to remove
 More energy is needed to overcome the attractive forces to remove electrons in n = 1
 Trends in Ionisation Energy
• Ionisation energies show periodicity - a trend across a period of
the Periodic Table

• The size of the ionisation energy is affected by four factors:

• Size of the nuclear charge
• Distance of outer electrons from the nucleus
• Shielding effect of inner electrons
• Spin-pair repulsion
 Factors that influence ionisation energy
1. The size of the nuclear charge
• As the proton number increases, the positive nuclear charge increases
• The greater the attractive force between the nucleus and the electrons
• More energy is needed to overcome these attractive forces if an electron is to be
removed
• IE increases as the proton number increases

2. Distance of outer electrons from the nucleus

• The force of attraction between positive and negative charges decreases rapidly as
the distance between them increases.
• Electrons in shells further away from the nucleus are less attracted to the nucleus
than those closer to the nucleus
• The further the outer electron shell is from the nucleus, the lower the IE
Factors that influence ionisation
energy
3. Shielding effect of inner electrons
• As all electrons are negatively charged, they repel each other
• Electrons in full inner shells repel electrons in outer shells.
• Full inner shells of electrons prevent the outer electrons feeling the full
nuclear charge.
• The greater the shielding of outer electrons by the inner electron shells, the
lower the attractive forces between the nucleus and the outer electrons
• The ionisation energy is lower as shielding effect increases

4. Spin-pair repulsion
• Electrons in the same atomic orbital in a sub-shell repel each other more
than electrons in different atomic orbitals.
• This increased repulsion makes it easier to remove an electron.
• Hence, ionisation energy is decreases
 Interpreting successive
ionization energies • First electron removed has a low first ionisation energy
 very easily removed from the atom.
 likely to be further away from the nucleus and well shielded by inner electron shells

• Second electron is much more difficult to remove than the first electron
 a big jump in the value of the ionisation energy
 suggests that the second electron is in a shell closer to the nucleus than the first
electron
 the 1st and 2nd ionisation energies suggest that sodium has one electron in its
outer shell

Graph of logarithm (log10) of the ionisation energy of sodium • From the second to the ninth electrons removed, there is only a gradual change in
against the number of electrons removed successive ionisation energies
 suggests that all these eight electrons are in the same shell

• The 10th and 11th electrons have extremely high ionisation energies
 suggests that they are very close to the nucleus.
 There must be a very great force of attraction between the nucleus and these
electrons and there are no inner electrons to shield them.
 The large increase in ionisation energy between the 9th and 10th electrons
confirms that the 10th electron is in a shell closer to the nucleus than the 9th
The arrangement of electrons in an atom of sodium can be deduced
electron
from the values of successive ionisation energies.
Figure below shows a sketch graph of the log base ten for
the successive ionisation energy. Use this graph to write out
the simple electronic configuration and predict the element
 Pattern in IE in the Periodic
Table (Patterns across a Period)
• The ionisation energy across a period increases
• Across a period the nuclear charge increases
• The atomic radius of the atoms to decrease, as the outer shell is pulled closer to the nucleus, so the
distance between the nucleus and the outer electrons decreases
• The shielding by inner shell electrons remain reasonably constant as electrons are being added to the
same shell
• It becomes harder to remove an electron as you move across a period; more energy is needed
• So, the ionisation energy increases

• There is a rapid decrease in ionisation energy between the last element in one period, and the first element in
the next period because:
• There is increased distance between the nucleus and the outer electrons as you have added a new shell
• There is increased shielding by inner electrons because of the added shell
• These two factors outweigh the increased nuclear charge
 Pattern in IE in the Periodic
Table (Patterns across a Period)
•There is a slight decrease in IE1 between beryllium and boron as
the fifth electron in boron is in the 2p subshell, which is further
away from the nucleus than the 2s subshell of beryllium
• Beryllium has a first ionisation energy of 900 kJ mol-1 as its
electron configuration is 1s2 2s2
• Boron has a first ionisation energy of 800 kJ mol-1 as its
electron configuration is 1s2 2s2 2px1

•There is a slight decrease in IE1 between nitrogen and oxygen

is due to spin-pair repulsion in the 2px orbital of oxygen
• Nitrogen has a first ionisation energy of 1400 kJ mol-1 as its
electron configuration is 1s2 2s2 2px1 2py1 2pz1
• Oxygen has a first ionisation energy of 1310 kJ mol-1 as its
electron configuration is 1s2 2s2 2px2 2py1 2pz1
 Pattern in IE in the Periodic
Table (Patterns down a Group)
• The first ionisation energy decreases as you go down a group in the Periodic Table

• For example, in Group 1 the values of IE 1 are:

• As you go down the group, the outer electron removed is from the same type of orbital but from a
successively higher principal quantum level: 2s for lithium, 3s for sodium and 4s for potassium

• Although the nuclear charge is increasing down the group there is less attraction between the outer
electron and the nucleus because:
 the distance between the nucleus and the outer electron increases
 the shielding effect by complete inner shells increases
 these two factors outweigh the increased nuclear charge
THANK YOU