Structure 1.

3: Electron Configurations

Guiding question: How can we model the energy states of electrons in atoms?

Structure 1.3.1
Emission spectra are produced by atoms emitting photons when electrons in excited states return
to lower energy levels.

Wave-particle duality of light

• White light consists of electromagnetic radiation of a specific range of wavelengths (see Figure 1).

white light

Figure 1: The electromagnetic spectrum

• Electromagnetic radiation is energy travelling in waves.

• The velocity of a wave is related to its frequency (f) and its wavelength (λ).
• Frequency and wavelength of electromagnetic waves are related by c = f λ where c is the speed of
light (3.00 x 108 m s-1).
• Hence, frequency and wavelength are inversely proportional (see Figure 2).

Figure 2: Relationship between frequency and wavelength

• Light can be considered to be not just a wave, but also a particle (wave-particle duality).
• Hence, light can be emitted or absorbed in discrete packets or quanta of energy (called photons).

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 Structure 1.3: Electron Configurations

• The energy of a light photon is given by E = h f where h is the Planck constant (6.63 x 10-34 J s).
• The energy of a photon is proportional to its frequency and hence, inversely proportional to
wavelength.
• The relationship between wavelength, frequency and energy across the electromagnetic spectrum
can be seen in Figure 3.

Figure 3: Wavelength, frequency and energy across the electromagnetic spectrum

• Within the visible region of the electromagnetic spectrum, different colours have different
wavelengths between 400 to 700 nm (see Figure 4) and hence, frequencies and energies, with red
having the longest wavelength and violet having the shortest wavelength.

Figure 4: Visible spectrum

Types of spectra
• One of the wave properties of light is that it can be diffracted through a thin diffraction slit or prism
resulting in a spectrum of colours of varying wavelengths and frequencies.
• If white light is simply diffracted as it is without involving any gaseous atomic sample, a continuous
spectrum is produced where the entire range of colours, wavelengths or frequencies are present (see
Figure 5).

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 Structure 1.3: Electron Configurations

Figure 5: A continuous spectrum

• When an atomic sample is vaporised and heated, it emits light of specific colours that can be
analysed for the frequencies it contains using an atomic spectrometer.

• This emitted light contains only specific colours, wavelengths or frequencies which appear as bright
lines in an emission line spectrum (see Figure 6).

Figure 6: An emission line spectrum

• Alternatively, white light can be passed through a vaporised and heated atomic sample which
absorbs light of specific colours, wavelengths or frequencies to produce an absorption line spectrum
consisting of black lines against a continuous spectrum (see Figure 7).

Figure 7: An absorption line spectrum

Emission spectra and flame test

• A flame test is an analytical procedure used in chemistry to detect the presence of certain elements,
primarily metal ions, based on each element's characteristic flame emission spectrum that results in
a distinctive flame colour (see Figure 8).

Figure 8: Flame test colour of some metals

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 Structure 1.3: Electron Configurations

• Figure 9 illustrates how the flame test is explained by the production of an emission spectrum
through electron excitation and de-excitation (or relaxation).

Figure 9: Production of an emission spectrum in a flame test of a metal

Structure 1.3.2
The line emission spectrum of hydrogen provides evidence for the existence of electrons in
discrete energy levels, which converge at higher energies.

• Hydrogen gas that is subjected to an energy source such as heat or electricity e.g. in a discharge
lamp, produces a line emission spectrum (see Figure 10).

Figure 10: Line emission spectra of hydrogen

• In the visible region of the electromagnetic spectrum, there are 4 lines observed that converge
towards higher energy i.e. become closer together.

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 Structure 1.3: Electron Configurations

• Niels Bohr, in 1913, proposed a model of an atom that helped to explain the observations. As spectra
of large multi-electron atoms are very complex and difficult to interpret, Bohr used the line emission
spectrum of hydrogen to develop his model. He stated that:
o Electrons can only occupy fixed energy levels; each energy level being assigned a
principal quantum number. The energy level closest to the nucleus being n = 1 and of
lowest energy.
o The energy of an electron is quantised; the electron may only have certain energies.
o Electrons can only absorb or emit energy of specific frequencies.
o When the electron occupies the energy level of lowest energy the atom is said to be in its
ground state. An atom can have only one ground state.
o If the electron occupies one of the higher energy levels, then the atom is in an excited state.
An atom has many excited states (see Figure 11).

Figure 11: Ground and excited states in Bohr’s model of the atom

• Therefore, emission spectra are produced when photons are emitted from atoms as excited electrons
return to a lower energy level.
• In particular, the line emission spectrum of hydrogen (known as the Balmer series) results from the
following electron transitions from higher energy levels to n = 2 (see Figure 12):
o 1st line: n = 3 → n = 2
o 2nd line: n = 4 → n = 2
o 3rd line: n = 5 → n = 2
o 4th line: n = 6 → n = 2

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 Structure 1.3: Electron Configurations

Figure 12: Line emission spectrum of hydrogen

• The lines converge at higher energies which suggest that the discrete energy levels also converge
at higher energies.

• Electron transitions can also occur from higher energy levels to other lower energy levels e.g. n =
1, n = 3 and n = 4 (see Figure 13).

Figure 13: Different series of spectral lines result from electron transitions
to different lower energy levels

• In the hydrogen atom, electron transitions to n = 1 result in a set of spectral lines in the ultraviolet
region of the electromagnetic spectrum (known as the Lyman series). As there is a large energy gap
between n = 1 and n = 2 etc, the photons emitted are of higher energies in this series.

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 Structure 1.3: Electron Configurations

• Electron transitions to n = 3 and n = 4 result in a set of spectral lines in the infrared region of the
electromagnetic spectrum (known as the Paschen and Brackett series respectively). As energy
levels converge at higher n values, the photons emitted are of lower energies in these series.
• Note that the names of the different series in the hydrogen line emission spectrum are not required.
• The line emission spectrum of hydrogen provides evidence for the existence of electrons in
discrete energy levels, which converge at higher energies.

Structure 1.3.3
The main energy level is given an integer number, n, and can hold a maximum of 2n2 electrons.

• The structure of the atom is pictured as consisting of a positively charged nucleus surrounded by
negatively charged electrons. The protons and neutrons are tightly packed together in the tiny
nucleus.
• The electrons move rapidly and orbit round the nucleus in increasingly higher energy levels that
converge at higher energies, held by electrostatic forces of attraction.
• In the Bohr model, the electrons are found at relatively great distances away from the nucleus in
clearly defined regions called energy levels or electron shells (see Figure 14).

• Figure 14: Electronic configuration in a Bohr model of the atom

• Each main energy level or electron shell is capable of holding a maximum number of electrons,
2n2, where n is an integer number denoting the main energy level or shell.
• The first shell which has the lowest energy is filled first, followed by the second shell and so on.
• Although the third shell can hold a maximum of 18 electrons, elements with atomic number 11-20
can hold up to a maximum of 8 electrons in the third shell because of the extra stability gained with
an octet structure.
• The way in which the electrons are arranged around the nucleus in an atom is very important
because it is this electron arrangement that determines the chemical properties of the atom.
• The furthest occupied shell from the nucleus is called the outer shell or valence shell.
• The electrons in this shell are called outermost electrons or valence electrons.

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 Structure 1.3: Electron Configurations

Structure 1.3.4
A more detailed model of the atom describes the division of the main energy level into s, p, d and
f sublevels of successively higher energies.

Structure 1.3.5
Each orbital has a defined energy state for a given electron configuration and chemical
environment, and can hold two electrons of opposite spin.
Sublevels contain a fixed number of orbitals, regions of space where there is a high probability of
finding an electron.

Limitations of the Bohr model of the atom

• The Bohr model of the atom worked well for hydrogen atoms but could not explain observations
of heavier elements. Complex emission lines of multi-electron atoms cannot be explained simply
by electrons transiting from one principal quantum number to another.
• Electrons in fact behave as wave-particles i.e. they exhibit behaviour of waves as well as of
particles, and the position of an electron in an energy level can therefore not be precisely known.
• In the 1920s, Louis de Broglie was the first to suggest that electrons could also possess wave-like
properties e.g. diffraction, the bending and spreading out of a wave on passing through a small
aperture.
• The realisation of the wave-particle duality of the electron enabled a method of describing the
electron structure based on the mathematics of waves.
• The Bohr model also violates the Heisenberg Uncertainty Principle, one of the cornerstones of
quantum mechanics, which states that both the exact position and momentum of an electron cannot
be known at the same time.
• This principle prompted scientists to think in terms of probabilities of finding electrons in certain
volumes of space.
• Schrodinger used de Broglie’s ideas to develop his wave equation in which he defined regions in
space or orbitals, around the nucleus, where there is a high probability (~90%) of finding an
electron of a given energy (see Figure 15).

Figure 15: Quantum mechanical model of the atom

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 Structure 1.3: Electron Configurations

Quantum (mechanical) model of the atom

• The mathematical solution to Schrodinger’s equation allows each electron in an atom to be uniquely
described by four different quantum numbers that gives the electron configuration of the atom.
o The first or principal quantum number describes the main energy level or shell (n = 1,2
…). The higher the number of n, the further from the nucleus it is.
o The second quantum number describes the type of sublevel(s) in that level. It describes
the shape of an orbital in that sublevel (see Figures 16 & 17).

Shell (n) Sublevel

1 s
2 s, p
3 s, p, d
4 s, p, d, f

Figure 16: Types of sublevels in each n level

Figure 17: Shapes of the s and p orbitals

o The third quantum number determines the number of orbitals of each type in a sublevel
(see Figures 18 & 19). For example, each set of p orbitals consists of three ‘dumb bell’
shaped orbitals (px, py and pz), 90° to each other about the nucleus.

Sublevel Number of orbitals

s 1
p 3
d 5
f 7

Figure 18: Number of orbitals of each type

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 Structure 1.3: Electron Configurations

Figure 19: s, p and d orbitals

o The fourth quantum number describes the spin of the electron. Electrons in one orbital
can either be spinning in one direction or in the opposite direction (see Figure 20).

Figure 20: Electrons of opposite spins in an orbital

• The Pauli Exclusion Principle states that no two electrons in the same atom can have exactly the
same four quantum numbers.
• Hence each orbital can contain a maximum of only two electrons.

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 Structure 1.3: Electron Configurations

Writing electronic configurations

• The following general rules are applied when writing electronic configurations for atoms and ions
(up to Z = 36) based on the quantum model of the atom:
o The Aufbau Principle - which states that the energy levels of lowest energy must be filled
first. Each set of orbitals are filled before electrons may enter into the next set (see Figure
21). Note that the 4s orbital is filled before the 3d orbital.

Figure 21: Filling of orbitals in the direction of the diagonal arrows starting from the 1s orbital

o The Pauli Exclusion Principle - which states that there can be no more than two electrons
in any orbital having opposite spins. This is represented in an orbital diagram in Figure 22.

Figure 22: An orbital (or arrow-in-box) diagram showing a pair of electrons of opposite spins

o Hund’s Rule - which states that orbitals of the same energy (i.e. orbitals in the same
sublevel) must be occupied singly before pairing occurs (see Figure 23).

Figure 23: Electrons fill orbitals in the same sublevel singly before pairing

• The electron configuration of an atom or ion can be represented in several ways (see Figure 24).
o Full electron configurations show all the electron-containing main energy levels and
sublevels (e.g. 1s22s22p63s23p4).
o Condensed electron configurations use an abbreviated inner core of a preceding noble gas
electron configuration followed by the remaining main energy levels and sublevels (e.g.
[Ne] 3s23p4).

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 Structure 1.3: Electron Configurations

o Orbital diagrams are used to represent the character and relative energy of orbitals. Orbital
diagrams refer to arrow-in-box diagrams, such as the one given below.

Figure 24: Ways of writing electronic configuration

• Among the elements up to Z = 36, Cu and Cr have exceptional electron configurations where their
4s orbitals are not completely filled before the 3d orbitals.
o Cu: 1s22s22p63s23p63d104s1
o Cr: 1s22s22p63s23p63d54s1
• For anions, electrons are added according to the general rules above.
• For cations of s-block and p-block elements, electrons are removed from the higher energy levels
first.
• For d-block elements, electrons are removed from the s orbital before the d orbitals as the d orbitals
are closer to the attraction of the nucleus due to their shape; thus it is easier to lose electrons from
the s orbital.

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 Structure 1.3: Electron Configurations

Structure 1.3.6
In an emission spectrum, the limit of convergence at higher frequency corresponds to ionization.

First ionization energy as evidence for arrangement of electrons in atoms

• Ionization energy is the energy required to remove each outermost electron from one mole of atoms
or ions of an element in its gaseous state.
• The first ionization energy (IE) is the energy required to remove one mole of electrons (to n = ∞)
from one mole of gaseous atoms to form one mole of gaseous positive ions.

e.g. Na(g) → Na+(g) + e- -- 1st IE

• The second IE is the energy required to remove the second outermost electron and so on.

e.g. Na+(g) → Na2+(g) + e- -- 2nd IE

• In an emission spectrum, the limit of convergence at higher frequency corresponds to the first
ionization energy.
• Consider the hydrogen emission spectrum (see Figure 25), as energy increases for each series the
lines get closer together until they converge.

H(g) → H+(g) + e-

n=1→n=∞

Frequency of the
limit of convergence

Figure 25: Limit of convergence corresponding to the first ionization energy of hydrogen

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 Structure 1.3: Electron Configurations

• This limit of convergence at higher frequency corresponds to the

o electron breaking away from the atom.
o H atom losing its one valence electron (in n = 1) and becoming a H+ ion.
• This is called ionization.
• The energy difference between this point and the ground state is called the first ionization energy.

Example 1
What is the first ionization energy of hydrogen given that ionization occurs above 13.6 eV?
(1 electron volt = 1.60217657 × 10-19 J)

energy needed to ionize 1 electron from a gaseous H atom = 13.6 x 1.602 x 10-19 J = 2.18 x 10-18 J
energy needed to ionize 1 mole of electrons from 1 mole of gaseous H atoms = 6.02 x 1023 x 2.18 x 10-
18
J mol-1 = 1310 kJ mol-1

Example 2
What is the first ionization energy of hydrogen given that the limit of convergence has a wavelength of
91.2 nm?

!" $.$& × )*-34 + &.** × )*8

energy needed to ionize 1 electron from a gaseous H atom = #
= ,).- × )*-9
= 2.18 x 10-18 J

energy needed to ionize 1 mole of electrons from 1 mole of gaseous H atoms = 6.02 x 1023 x 2.18 x 10-
18
J mol-1 = 1310 kJ mol-1

• First ionization energy values show a periodic trend. There is a ‘general increase’ across a period
before the value drops dramatically for the start of another period (see Figure 26).
• The values get smaller down groups as the electron removed comes from an orbital further from
the nucleus i.e. higher main energy levels which experience more electron shielding.

Figure 26: Periodic trend in first ionization energies

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 Structure 1.3: Electron Configurations

• The trends and discontinuities in first ionization energy across a period can be explained by the
electron configurations of the atoms of the elements, and thus provide evidence for the existence of
main energy levels and sublevels in atoms (see Figure 27 and Table 1).

Figure 27: Electron configurations related to trends and discontinuities in

first ionization energy of the first 12 elements

Electron
Element Explanation of trend in 1st IE
configuration
Despite having a nuclear charge of only 1+, hydrogen has a
Hydrogen 1s1 relatively high first ionization energy as its electron is closest
to the nucleus and has no shielding.
Helium has a much higher value because of the extra proton
Helium 1s2 in the nucleus. The additional charge provides a stronger
attraction for the electrons making them harder to remove.
There is a substantial drop in the value for lithium. This is
because the extra electron has gone into an orbital in the next
higher energy level. Despite the increased nuclear charge, the
Lithium 1s22s1 effective nuclear charge is less because of the shielding
effect of filled inner 1s energy level. The 2s electron is also
further away from the nucleus. It is held less strongly and
needs less energy for removal.

Table 1: Explanation of the trend in 1st IE for Z = 1 to 12

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 Structure 1.3: Electron Configurations

Electron
Element Explanation of trend in 1st IE
configuration
The value for beryllium is higher than for lithium due to the
2 2
Beryllium 1s 2s increased nuclear charge. There is no extra shielding as the
extra electron is added into the same sublevel.
There is a drop in the value for boron (the first discontinuity
in the general trend). This is because the extra electron has
gone into one of the 2p orbitals which are of higher energy
than the 2s orbital. The increased shielding by the filled 2s
Boron 1s22s22px1
energy level makes the electron easier to remove. It was
evidence such as this that confirmed the existence of
sublevels. If there had not been any sublevel, the value would
have been higher than that of beryllium.
The value increases again for carbon due to the increased
nuclear charge. The extra electron does not pair up with the
previous one in the same orbital but occupies another of the
Carbon 1s22s22px12py1
2p orbitals. This gives a lower energy configuration because
there is less repulsion between the negatively charged
particles. This is known as Hund’s Rule.
The value increases again for nitrogen due to the increased
2 2 1 1 1
Nitrogen 1s 2s 2px 2py 2pz nuclear charge. As before, the extra electron goes into the
vacant 2p orbital. There are now three unpaired electrons.
There is a drop in the value for oxygen (the second
discontinuity in the general trend). The extra electron has
paired up with one of the electrons already in one of the 2p
Oxygen 1s22s22px22py12pz1
orbitals. The repulsive force between the two paired-up
electrons means that less energy is required to remove one of
them.
The value increases again for fluorine due to the increased
Fluorine 1s22s22px22py22pz1
nuclear charge. The 2p orbitals are almost full.
The value increases again for neon due to the increased
Neon 1s22s22px22py22pz2 nuclear charge. The 2p orbitals are now full so the next
electron in will have to go into the higher energy 3s orbital.

Table 1 (continued): Explanation of the trend in 1st IE for Z = 1 to 12

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 Structure 1.3: Electron Configurations

Electron
Element Explanation of trend in 1st IE
configuration
There is a substantial drop in the value for sodium. This is
because the extra electron has gone into an orbital in the next
Sodium 1s22s22px22py22pz23s1 higher energy level. Despite the increased nuclear charge, the
effective nuclear charge is less because of the shielding effect
of filled inner 1s, 2s and 2p energy levels.
The value for magnesium is higher than for sodium due to the
Magnesium 1s22s22px22py22pz23s2 increased nuclear charge. There is no extra shielding. The
trend is similar to that at the start of period 2.

Table 1 (continued): Explanation of the trend in 1st IE for Z = 1 to 12

Structure 1.3.7
Successive ionization energy (IE) data for an element give information about its electron
configuration.

Successive ionization energy as evidence for arrangement of electrons in atoms

• Successive ionization energy data for an element give information that shows relations to electron
configurations.
• For example, the successive ionization energies (IEs) of boron in kJ mol-1 is given in Table 2 and
plotted in Figure 28.

First Second Third Fourth Fifth

807 2430 3670 25030 32830

Table 2: Successive ionization energies of boron

Figure 28: Successive ionization energies of boron

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 Structure 1.3: Electron Configurations

• From the first to the third IEs and from the fourth to the fifth IEs, there is gradual increase in value
because it is increasingly difficult to remove an electron from an increasingly positively charged
ion.
• The large jump between the third and fourth IEs suggests that the fourth electron is being removed
from a lower energy level that is closer to the nucleus i.e. n = 1 instead of n = 2.
• There are 2 occupied energy levels in boron: 2 electrons in n = 1 and 3 electrons in n = 2.
• Therefore, boron is in group 13 of the periodic table as it has 3 valence electrons.
• The group of an element can thus be deduced from its successive ionization energy data.
o Large jumps in IEs signify different main energy levels.
o The number of successive IEs between the large jumps is the number of electrons in that
main energy level and the electron configuration can thus be deduced.
o The number of valence electrons and hence the group to which the element is in can be
deduced from the number of electrons removed before the first large jump in IE.

- End -

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 Structure 1.3: Electron Configurations

Notes:
Reflect on and answer the guiding question at the start of this sub-topic:

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