Electrons in Atoms.

Electrons in atoms
Momtahina Tabassum
Chemistry Teacher
Simple electronic structure
• Electrons are arranged outside the nucleus in energy levels or
quantum shells.
• These principal energy levels or principal quantum shells (symbol n)
are numbered according to how far they are from the nucleus.
• The lowest energy level, n = 1, is closest to the nucleus, the energy
level n = 2 is further out, and so on.
• The electrons in quantum shells further away from the nucleus have
more energy and are held less tightly to the nucleus.
• The arrangement of electrons in an atom is called its electronic
structure or electronic configuration.
Electron holding capacities
■ Shell 1: up to 2 electrons
Evidence for electronic structure
• Ionisation energy, ΔHi
By firing high-speed electrons at atoms, scientists can work out how
much energy has to be supplied to form an ion by knocking out one
electron from each atom.
The energy change that accompanies this process is called the
ionisation energy.
• First ionisation energy, IE1: The energy needed to remove 1 mole of
electrons from 1 mole of atoms of an element in gaseous state to
form 1 mole of gaseous 1+ ions.
Evidence for electronic structure
• Second ionisation energy, IE2: The energy needed to remove 1 mole
of electrons from 1 mole of gaseous 1+ ions to form 1 mole of
gaseous 2+ ions.
• Third ionisation energy, IE3: The energy needed to remove third
electron from each ion in 1 mole of gaseous 2+ ions.
• We can continue to remove electrons from an atom until only the
nucleus is left. We call this sequence of ionisation energies, successive
ionisation energies.
Example:
1st ionisation energy: Li(g) → Li+(g) + e-
2nd ionisation energy: Li+(g) → Li2+(g) + e-
3rd ionisation energy: Li2+(g) → Li3+(g) + e-
Successive ionisation energies
• For each element, the successive ionisation energies increase.
• This is because the 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. Therefore more energy is
needed to overcome these attractive forces.
Successive ionisation energies for the first 11
elements
Successive ionisation energies for the first 11 elements in the Periodic Table (values in kJmol–1)
elements
elements
elements
elements
elements
elements
elements
elements
elements
elements
Students’ participation
1. Write equations that describe:
a. the 1st ionisation energy of calcium
b. the 3rd ionisation energy of potassium
c. the 2nd ionisation energy of lithium
d. the 5th ionisation energy of sulfur.
2. The 2nd ionisation energy of nitrogen is 2860kJmol–1. The 3rd
ionisation energy of nitrogen is 4590kJmol–1. Explain why the 3rd
ionisation energy is higher.
Factors that influence ionisation energies
1. The size of the nuclear charge
As the atomic number (number of protons) increases, the
positive nuclear charge increases. The bigger the positive
charge, the greater the attractive force between the nucleus
and the electrons. So, more energy is needed to overcome
these attractive forces if an electron is to be removed.
■ In general, ionisation energy 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.
So, 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 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 full nuclear
charge being felt by the outer electrons. This is called
shielding.
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 the number of full
electron shells between the outer electrons and the
nucleus increases.
3. Spin-pair repulsion
Electrons in the same atomic orbital in a sub-shell repel each other
more than electrons in the different atomic orbitals. This increased
repulsion makes it easier to remove an electron. So first ionisation
energy decreased.
Interpreting successive ionisation energies
• Graph of logarithm
(log10) of
ionisation energy
of sodium against
the number of
electrons removed
• The first electron removed has a low 1st ionisation energy,
when compared with the rest of the data. It is very easily
removed from the atom. It is therefore likely to be a long way
from the nucleus and well shielded by inner electron shells.
• The second electron is much more difficult to remove than

the first electron. There is a big jump in the value of the
ionisation energy. This suggests that the second electron is
in a shell closer to the nucleus than the first electron. Taken
together, the 1st and 2nd ionisation energies suggest that
sodium has one electron in its outer shell.
• From the second to the ninth electrons removed there is
only a gradual change in successive ionisation energies. This
suggests that all these eight electrons are in the same shell.
• The 10th and 11th electrons have extremely high ionisation

energies, when compared with the rest of the data. This
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 electron.
Patterns in ionisation energies across a period
1. There is a general increase in IE1 across a period.
➢ This applies to Period 1 (hydrogen and helium), Period 2 (lithium to neon)
and also to other periods.
➢ As you go across a period the nuclear charge increases. But the electron
removed comes from the same shell. The ionisation energy changes across
period because:
i. the nuclear charge increases
ii. the distance between the nucleus and the outer electron remains reasonably
constant
iii. the shielding by inner shells remains reasonably constant.
iv. So, the force of attraction between the positive nucleus and the outer negative
electrons increases across the period
2.There is a rapid decrease in ionisation energy between the last element in
one period and the first element in the next period.
The IE1 for lithium is much smaller than the IE1 for helium. Helium has two
electrons. These are in the first quantum shell. But lithium has three electrons.
The third electron must go into the next quantum shell further away from the
nucleus. So, the force of attraction between the positive nucleus and the outer
negative electrons decreases because:
i. the distance between the nucleus and the outer electron increases
ii. the shielding by inner shells increases
iii. these two factors outweigh the increased nuclear charge.
3. There is a slight decrease in IE1 between beryllium and boron. Although boron
has one more proton than beryllium, there is a slight decrease in IE1 on
removal of the outer electron. Beryllium has the electronic structure 1s2 2s2
and boron has the electronic structure 1s2 2s2 2p1. The fifth electron in boron
must be in the 2p subshell, which is slightly further away from the nucleus than
the 2s subshell. There is less attraction between the fifth electron in boron and
the nucleus because:
i. the distance between the nucleus and the outer electron increases slightly
ii. the shielding by inner shells increases slightly
iii. these two factors outweigh the increased nuclear charge the shielding by inner shells
increases
4. There is a slight decrease in IE1 between nitrogen and oxygen.
Oxygen has one more proton than nitrogen and the electron removed is in the
same 2p subshell.
• The electron removed from the nitrogen is from an orbital that contains an
unpaired electron. The electron removed from the oxygen is from the orbital that
contains a pair of electrons. The extra repulsion between the pair of electrons in
this orbital results in less energy being needed to remove an electron.
• So, IE1 for oxygen is lower, because of spin-pair repulsion.
• N : 1s²2s²2px¹2py ¹2pz¹ O : 1s²2s²2px²2py ¹2pz¹
❖ The decrease in first ionisation energy between phosphorus and sulphur has the same
reason, except that everything is happening at the third energy level.
P : 1s²2s²2p⁶3s²3px¹3py ¹3pz¹ S : 1s²2s²2p⁶3s²3px²3py ¹3pz¹

Patterns in ionisation energies 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 IE1 are:
■ Li = 519 kJ mol–1
■ Na = 494 kJ mol–1
■ K = 418 kJ mol–1
■ Rb = 403 kJ mol–1
• 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 from lithium, 3s for sodium and 4s for potassium.
Patterns in ionisation energies down a group
• Although the nuclear charge is increasing down the group there is less
attraction between the outer electron and the nucleus because:
i. the distance between the nucleus and the outer electron increases
ii. the shielding by complete inner shells increases
iii. these two factors outweigh the increased nuclear charge.
A graph of the first ionisation energies
plotted against atomic number
Summary
• We can use successive ionisation energies in

this way to:
■ predict or confirm the simple electronic
configuration
of elements
■ confirm the number of electrons in the
outer shell of an
element and hence the group to which the
element belongs.
■ deduce which group an element belong to
in the Periodic Table
Principle quantum shell
• Electrons are arranged outside the nucleus in energy levels or principle
quantum shell, n.
• The principal quantum shells are numbered according how far are they from the
nucleus
• The lowest energy level, n = 1 is closest to the nucleus, the energy level n = 2 is
further out, and so on.
Quantum subshells
• The principal quantum shells, apart from the first, are split into subshells
(sublevels).
• Each principal quantum shell contains a different number of subshells.
The subshells are distinguished by the letters s, p or d.
• There are also f subshells for elements with more than 57 electrons.
Quantum subshells
• In any principal quantum shell, the energy of the electrons in the
subshells increases in the order s < p < d.
• The maximum number of electrons that are allowed in each subshell is: s
= 2 electrons, p = 6 electrons, d = 10 electrons.
■ The first principal quantum level, n = 1, can hold a maximum of 2
electrons in an s subshell.
■ The second principal quantum level, n = 2, can hold a maximum of 8
electrons: 2 electrons in the s subshell and 6 electrons in the p subshell.
■ The third principal quantum level, n = 3, can hold a maximum of 18
electrons: 2 electrons in the s subshell, 6 electrons in the p subshell and
10 electrons in the d subshell.
Quantum subshells
• The order of the subshells in terms of
increasing energy does not follow a
regular pattern of s then p then d after the
element argon.
• The order of subshells after argon appears
to overlap. The next element after argon is
potassium.
The subshells for the first four principal quantum shells

.
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 subshell must be:
s – one orbital {s}
p – three orbitals {px, py, pz}
d – five orbitals {dxy, dyz, dxz, dx²-y², dz²}
Shapes of the orbitals
• Each orbital has a 3D
shape. Within this shape
there is a high probability
of finding the electron or
electrons in the orbital.
The s orbital
1) All the s orbitals are spherical and non-directional.

2) The shaded region represents the region in which the chance of finding
the s electron is more than 95%.
3) The size of the s orbital increases in the order 1s < 2s < 3s < 4s.
The p orbital
1) All the p orbitals are dumb-bell shaped and directional.
2)Going to a higher energy level, the 'lobes' of the p orbital become longer
Shapes of the orbitals
• The d orbitals are more complex in shape and
arrangement in space.
The shape of a dz2 orbital

Electronic Configuration
❏ Ways to represent electronic configuration-
Electronic configuration describes how the electrons in an atom/ion are
arranged in their shells, sub-shells and orbitals.
Filling the shells and orbitals
• The most stable electronic
configuration (electronic structure)
of an atom is the one that has the
lowest amount of energy.
• The subshell with the lowest
energy, the 1s, is therefore filled
first, followed by those that are
successively higher in energy.
• The order of the subshells in terms
of increasing energy does not
follow a regular pattern of s then p
then d after argon, where the 3p
subshell is full.
Representing electronic configurations
• Hydrogen has one electron. This can go into the 1s orbital, as this can
hold a maximum of two electrons. So, the electronic structure of
hydrogen is 1s1.
Electronic configurations for the first 18 elements in the Periodic Table
Electronic configurations
■ Electronic configuration of potassium- Potassium has the electronic structure
1s2 2s2 2p6 3s2 3p6 4s1.
The outer electron goes into the4s subshell rather than the 3d subshell because
the 4s is below the 3d in terms of its energy,4s has a lower energy level than 3d.
■ Filling the 3d subshell- After calcium, a new subshell becomes occupied.

The next electron goes into a 3d subshell rather than a 4p subshell. So scandium
has the electronic configuration [Ar] 3d1 4s2. This is because electrons occupy
the orbitals with the lowest energy – the 3d subshell is just above the 4s
subshell but below the 4p subshell.
This begins a pattern of filling the 3d subshell ending with zinc. Zinc has the
electronic configuration [Ar] 3d10 4s2.
■ Chromium and copper- The electronic configurations of chromium and
copper do not follow the expected pattern.
❖ For chromium, the electronic configuration is [Ar]3d⁵4s¹ instead of
[Ar]3d⁴4s². This is because orbitals that are fully filled or half filled
have extra stability due to their symmetrical charge distribution.
❖ Copper has the electronic configuration [Ar]3d10 4s1 (rather than the
expected [Ar]3d9 4s2) .The reason is the same.
for some of the elements
19 to 36, where [Ar] is the
electronic structure of
argon 1s2 2s2 2p6 3s2 3p6
Orbitals and the Periodic Table
• The arrangement of elements in the Periodic Table reflects the
electronic structure of the elements.
• The Periodic Table can be split into blocks of elements.
Orbitals and the Periodic Table
• Elements in Groups 1 and 2 have outer electrons in an s subshell
• Elements in Groups 3 to 18 (apart from He) have outer electrons in a
p subshell.
• Elements that add electrons to the d subshells are called the d-block
elements. Most of these are transition elements.
Filling the orbitals
• A useful way of representing electronic configurations is a diagram
that places electrons in boxes
The electronic configuration of boron in box form.

• Each box represents an atomic orbital.
• An electron is represented by an arrow.
• The direction of the arrow represents the ‘spin’ of the electron. (We
imagine an electron rotating around its own axis either in a clockwise
or anticlockwise direction.)
• 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.
• Electrons in the same region of space repel each other because they
have the same charge (spin-pair repulsion).
• So wherever possible,
electrons will occupy separate orbitals in the same subshell 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 subshell. The spins are then opposite to
minimise repulsion.
Free radicals
• A free radical is a species with one or more unpaired electrons.
• As example of a free radical is an isolated chlorine atom which has the
electronic configuration 1s2 2s2 2p6 3s2 3p5.
• 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..
Electronic configuration of ions
• Positive ions are formed when electrons are removed from atoms. The
sodium ion, Na+ (proton number = 11), has 10 electrons.
• So, its electronic configuration is 1s2 2s2 2p6.
• Negative ions are formed when atoms gain electrons. The sulfide ion, S2–
(proton number = 16), has 18 electrons.
• Its electronic configuration is 1s2 2s2 2p6 3s2 3p6.
• In general, electrons in the outer subshell are removed when metal ions
form their positive ions. However, the d-block elements behave slightly
differently.
For example,
Ti atom- 1s2 2s2 2p6 3s2 3p6 3d2 4s2; Ti2+ ion- 1s2 2s2 2p6 3s2 3p6 3d2.
Cr atom- 1s2 2s2 2p6 3s2 3p6 3d5 4s1; Cr3+ ion- 1s2 2s2 2p6 3s2 3p6 3d3.
Periodic patterns if atomic and ionic radii
• Atomic radius- The atomic radius increases down any group.
• This is because, going down the group, each successive element has one more
shell of electrons which is further from the nucleus.
• 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.
The atomic radius decreases across any period.
• This is because the number of protons, and therefore the nuclear charge,
increases by one with each successive element. 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.
Periodic patterns if atomic and ionic radii
• lonic radius- The ionic radius increases down any group (for ions with
the same charge).
• Going down the group, each successive element has one more shell of
electrons which is further from the nucleus.
• The increased effect of inner shell electrons shielding the outer shell
electrons is more important than the effect of increased nuclear
charge.

Electrons in Atoms.

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Electrons in Atoms.

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Electrons in atoms

■ In general, ionisation energy increases as the proton

• The second electron is much more difficult to remove than

• The 10th and 11th electrons have extremely high ionisation

P : 1s²2s²2p⁶3s²3px¹3py ¹3pz¹ S : 1s²2s²2p⁶3s²3px²3py ¹3pz¹

• We can use successive ionisation energies in

The subshells for the first four principal quantum shells

1) All the s orbitals are spherical and non-directional.

The shape of a dz2 orbital

■ Filling the 3d subshell- After calcium, a new subshell becomes occupied.

The electronic configuration of boron in box form.

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