Atomic Structure Notes 1

ATOMIC STRUCTURE COMPILED BY S MAPURANGA
Subshells and atomic orbitals
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.
 Figure 1.1 shows the subshells for the first four principal quantum levels.
Figure 1. 1 The subshells for the first four principal quantum shells.
 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.
NOTE: You will also notice from Figure 3.6 that 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. Potassium’s outer electron is in the 4s, not
in the 3d, subshell.
 The first element with an electron in the 3d subshell is element 21, scandium.
Atomic orbitals
 Each subshell 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 subshell must be:
s – One orbital
p – Three orbitals
d – Five orbitals.
SHAPES OF THE ORBITALS

 Each orbital has a three-dimensional shape. Within this shape there is a high
probability of finding the electron or electrons in the orbital.
 Figure 1.2 shows how we represent the s and p orbitals.
Figure 1. 2 Shapes of s and p orbitals
 Representations of orbitals (the position of the nucleus is shown by the black dot):
a. s orbitals are spherical;

b. p orbitals, px, py and pz, have ‘lobes’ along the x, y and z axes.
 An s orbital has a spherical shape.

 The 2s orbital in the second principal quantum shell has the same shape as the 1s
orbital in the first quantum shell.
 They are both spherical, but electrons in the 2s orbital have more energy than
electrons in the 1s orbital.
 There are three 2p orbitals in the second quantum shell.
 Each of these has the same shape. The shape is like an hourglass with two ‘lobes’.
 The three sets of ‘lobes’ are arranged at right angles to each other along the x, y and z
axes.
 Hence the three 2p orbitals are named 2px, 2py and 2pz. The three 2p orbitals have
the same energy as each other.
 There are also three 3p orbitals in the third quantum shell. Their shapes are similar to
the shapes of the 2p 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 order in which the subshells are filled depends on their relative energy.
 The subshell with the lowest energy, the 1s, is therefore filled first, followed by those
that are successively higher in energy
 Figure 1.3 shows the order of filling orbitals
Figure 1. 3 Diagram to show the order in which orbitals are filled up to shell n = 4.
Electronic configurations
 Helium has two electrons. Both electrons can go into the 1s orbital, as this can hold a
maximum of two electrons. So, the electronic structure of helium is 1s2.
 Lithium has three electrons. The 1s orbital can only hold a maximum of two electrons
so the third electron must go into the next highest subshell, the 2s. So, the electronic
structure of lithium is 1s2 2s1.
 Electrons are added one by one for successive elements, filling each subshell in order
of increasing energy.
You should note the following:

Electronic configuration of potassium
 Potassium has the electronic structure 1s2 2s2 2p6 3s2 3p6 4s1. The outer electron goes
into the 4s subshell rather than the 3d subshell because the 4s is below the 3d in terms
of its energy.
 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] 3d 1 4s2.
 [Ar] represents the electronic configuration of argon: 1s2 2s2 2p6 3s2 3p6
 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
Chromium and copper

 The electronic configurations of chromium and copper do not follow the expected
pattern.
 Chromium has the electronic configuration [Ar] 3d5 4s1 (rather than the expected [Ar]
3d4 4s2).
 Copper has the electronic configuration [Ar] 3d10 4s1 (rather than the expected [Ar]
3d9 4s2). You will have to learn that these two elements are exceptions to the pattern.
Gallium to krypton
 The electrons add to the 4p subshell because this is the next highest energy level
above the 3d.
Filling the orbitals

A useful way of representing electronic configurations is a diagram that places electrons in
boxes (Figure 1.4).
Figure 1. 4 The electronic configuration of boron in box form.
 Electrons in the same region of space repel each other because they have the same
charge.
 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
 Figure 1.5 shows the electronic structures of carbon, nitrogen and oxygen to illustrate
these points.
Figure 1. 5 When adding electrons to a particular subshell, the electrons are only paired
when no more empty orbitals are available.
Orbitals and the Periodic Table

The Periodic Table can be split into blocks of elements (Figure 1.6).
Figure 1. 6 Some of the blocks of elements in the Periodic Table.
Electronic configuration of ions

 Positive ions are formed when electrons are removed from atoms.
 Note that, in general, electrons in the outer subshell are removed when metal ions form
their positive ions.
 However, the d-block elements behave slightly differently.
 When atoms of a d-block element lose electrons to form ions, the 4s electrons are lost
first.
 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
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.
 The 1st 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.
 Consider the first ionisation of magnesium :
Mg(g) → Mg + (g) + e
 Ionisation energies are measured under standard conditions.
 The general symbol for ionisation energy is ΔHi.
 Its units are kJ mol–1.
 The symbol for the 1st ionisation energy is ΔHi1. Using calcium as an example:
 1st ionisation energy: Ca(g) → Ca+(g) + e
 ΔHi1 = 590 kJ mol–1
 Second ionisation energy is for one mole of each ion in gas phase
 For example consider the second ionisation energy of calcium
Ca+ ⟶ Ca2+ (g) + e
ΔHi2 = 1150 kJ mol–1
Question
Construct an equation for the 3rd ionisation energy for calcium
 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.
 There is a big difference between some successive ionisation energies. For nitrogen this
occurs between the 5th and 6th ionisation energies. For sodium the first big difference
occurs between the 1st and 2nd ionisation energies. These large changes indicate that
for the second of these two ionisation energies the electron being removed is from a
principal quantum shell closer to the nucleus.
Table 1. 1 Successive ionisation energies for the first 11 elements in the Periodic Table.

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ATOMIC STRUCTURE COMPILED BY S MAPURANGA

Subshells and atomic orbitals

 The second principal quantum level, n = 2, can hold a maximum of 8 electrons: 2

 The order of subshells after argon appears to overlap

SHAPES OF THE ORBITALS

Figure 1. 2 Shapes of s and p orbitals

a. s orbitals are spherical;

 An s orbital has a spherical shape.

Filling the shells and orbitals

You should note the following:

Chromium and copper

Filling the orbitals

Figure 1. 4 The electronic configuration of boron in box form.

Orbitals and the Periodic Table

Figure 1. 6 Some of the blocks of elements in the Periodic Table.

Electronic configuration of ions

Ti atom: 1s2 2s2 2p6 3s2 3p6 3d2 4s2

Cr atom: 1s2 2s2 2p6 3s2 3p6 3d5 4s1

Evidence for electronic structure

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