Topic 12 ATOMIC STRUCTURE: Electronic configuration

12. 1. Electrons in atoms

Essential idea: The quantized nature of energy transitions is related to the energy states of
electrons in atoms and molecules.

Understandings
In an emission spectrum, the limit of convergence at higher frequency corresponds to the first
ionization energy.
Trends in first ionization energy across periods account for the existence of main energy levels and
sub-levels in atoms.
Successive ionization energy data for an element give information that shows relations to electron
configurations.
Applications and skills
Solving problems using = h.
Calculation of the value of the first ionization energy from spectral data which gives the wavelength
or frequency of the convergence limit.
Deduction of the group of an element from its successive ionization energy data.
Explanation of the trends and discontinuities in first ionization energy across a period.

Calculations of energies

As seen in the SL section all electromagnetic radiation transfers energy in fixed or discrete amounts that
are called photons (parcels of energy).
The frequency, v, of electromagnetic waves and the energy, E, of the photons are connected by an
equation introduced by Planck:
E = hv E = energy (of photon) (in joules)
h = Plancks constant (6.626 x 10-34 J s)
v = frequency (in s-1)

In the case of wave information being giving in terms of wavelength instead of frequency than the above
equation needs to be modified.
As c = v, v in Planks equation can be substituted by 1/; the equation becomes E = hc/
Remember also that some energy values are expressed in joules per mole; this means that any energy
value might need to multiplied or divided by 6.02 x 1023.

First ionization energy (IE1)

The first ionization energy of an atom is the minimum energy needed to remove one electron from 1
mole of gaseous atoms to make gaseous cations as shown by the equation below:

X (g) X+ (g) + e-

If an electron in an atom obtains enough energy it jumps or transitions beyond the highest energy level
and becomes a free electron; the atom itself becomes a positive ion.
In the hydrogen atom this electron transition is represented as follows: n = 1 to n = . The notation n =
refers to an energy level just beyond the highest energy level in the atom, it refers to the world
outside the atom beyond the control of the nucleus; any electron outside an atom has no potential
energy (energy = 0).

The first electron that is removed is the electron on the highest energy level in the atom with the atom in
its ground state; this electron needs the least amount of energy. In the case of hydrogen as there is only
1 electron, the removed electron is the electron that is on the first energy level, n=1.

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The first ionization energy can be determined from the frequency at the point in the line emission
spectrum series where the lines converge at the high frequency end. In the case of hydrogen this is in
the high frequency end in the Lyman series. The Lyman series is formed by electron transition involving
hydrogens highest energy level n = 1 in its ground state.

At the high frequency end of a series the lines are so close together that they form a continuous band of
radiation in which no separate lines can be recognized. The start of this band is called the convergence
limit and at this point the atom has lost all control over the electron. The frequency at which the
convergence limit corresponds to the first ionization energy and can be determined as shown below.

In the hydrogen atom the frequency at the convergence limit in the Lyman series corresponds to the first
ionization energy.

Determining the ionization energy.

The frequencies in the table below represent electron transitions between different levels and n=1.
These frequencies result in lines in the ultraviolet spectrum.

Frequency, v Transition to 1. Work out the difference in frequency, v, between successive

(in 1014 s-1) which lines in the Lyman series for hydrogen
frequency
corresponds 2. Plot a graph of v against frequency use the value of the
24.66 n = 2 to n =1 lower frequency for plotting v.
29.23 n = 3 to n =1 3. Use your graph to estimate the frequency when v becomes
30.83 n = 4 to n =1 0.
31.57 n = 5 to n =1 4. v becomes 0 when the difference in energy between the
31.97 n = 6 to n =1 electronic energy levels becomes 0. Use the relationship
32.21 n = to n =1 E=hv to find the energy which corresponds to the frequency
32.37 n = 8 to n =1
when v becomes 0. This energy is the first ionization energy
for hydrogen but this is usually expressed in kJ mol-1.

The first ionization energy is the energy needed to transition a hydrogens electron in an atom in the
ground state from n = 2 to n = .

More about the first ionization energy (IE1):

the more strongly the electron is attracted to the nucleus, the greater the amount of energy needed
ionization energy is usually measured in kilojoules per mole (kJ mol-1) of atoms;
ionization energies are positive values (endothermic process) as energy is needed to remove an
electron.

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First ionization energies: evidence for main energy levels, sub-levels and Hunds rule

observation evidence for:

There is a repeated pattern Existence for main energy levels:

(=periodic trend) of highest values for The large drop is caused by the most loosely held electron
noble gases followed by a large drop being on an energy level much further from nucleus.
for alkali metals. Peaks of noble gases/troughs of alkali metals also get lower
Peaks of noble gases/troughs of as the most outer electron is on a higher main energy level
alkali metals also get lower as atomic same periodic trend but at lower energy because the trend
number increases. occurs at a higher energy level in the atom.
Overall increase in first ionization Existence of main energy level:
energies across a period. Electrons are added to same main energy level but nuclear
charge increases greater attraction more energy needed.
Decrease in ionization energy Existence of main energy level:
between He and Li (and Ne and Na; The large drop from He to Li can be explained in that the 3rd Li
Ar and K and so on) electron (the electron in the highest energy level) is at a higher
main energy level than the 2nd electron (the electron in the
highest energy level) in He; any large decrease in ionization
energy means that the electron is in a higher energy level/less
strongly attracted/further away from the nucleus.
There is no continuous increase Existence of sub-level:
between Li and Ne (this period of 8 If all the valence electrons of the elements in the second
elements is made up of smaller period were in the same main energy level (n=2), a normal
groups of 2, 3 and 3) steady rise in first ionisation energy would be expected. This
is because the electrons would be attracted more strongly by
the greater nuclear charge and decrease in atomic radius.
However, instead there are 2 drops in ionisation energy
between Li and Ne: not all of the most outer electrons of the 8
elements in that period 2 are the same; they are not on the
same energy level.
A decrease from Be to B; this Existence of sub-level:
decrease occurs after the second The drop from Be to B indicates that the 5th B electron is at
element in the period a higher energy level than the 4th Be electron both of which
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 should be on the 2nd main energy level; this has been
explained by the fact that the 5th B electron is on a higher
sub-level within the 2nd main energy level;
The lowest level at this main energy level is full after 2
electrons.

There are 6 elements between Be The second level in this main energy level can hold 6
and Ne (Ne including) after which electrons
there is again a great decrease
A decrease from N to O (also P to S) Existence of sub-level:
The electron arrangement ensures that the most outer
electron in oxygen is at a higher energy level than the most
outer electron in nitrogen. This is the case because the
electron removed in O is a paired electron (two electrons in
same orbital) and this causes greater repulsion and less
attraction Hunds rule.

Successive ionization energies

Energy needed to remove second, third,... electrons from 1 mole of gaseous ions, e.g.

second ionization energy (IE2) X+ (g) X2+ (g) + e-

third ionization energy (IE3): X2+ (g) X3+ (g) + e-

The lower the energy level an electron is on, the closer it is to the nucleus, the more strongly it is
attracted, the more ionization energy is needed;

In the same atom, successive ionization energies of electrons in the same energy level increase
because mainly the first electron is removed from an atom whilst the second and other successive
electrons are removed from ions with an increasing positive charge; electrons are removed by
applying a positive charge but this needs to overcome increased repulsion from ion. Other reasons
for increase in ionization energy of electrons in same energy level include:

o the electron-electron repulsion decreases (this repulsion puts electrons onto higher energy
levels) and this increases the attraction from the nucleus.
o nucleus has greater effect on smaller number of electrons and they are held more tightly.
o lower shielding effect from fewer inner electrons.

Successive ionization also increases if the next electron is on a lower energy level/closer to the
nucleus.

Successive ionization energies: evidence for the main energy levels and the number of electrons
that can occupy an energy level.

All the successive ionization energies for the same element can be shown on a graph of successive
ionization energies against electrons removed. The successive ionization

Find the graph showing successive ionization energies for sodium. How does it show evidence for the
existence of main energy levels? Check your textbook to find out why logarithm scales are used
In your class book, sketch the graph of successive ionization energies for aluminium using a logarithm
scale. A logarithm scale is used so that the large differences between the ionization energies can be
shown onto the same graph. On your graph identify the different electrons using the main energy,
sublevel and orbital annotation.

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Observations of trends in successive Explanation:
ionization energies of aluminium

3 electrons (3s2 and 3p1 ; have a much smaller These electrons must be on a much higher energy
ionization energy than the other remaining level than the other 10 electrons in the atom; most of
electrons which means they need a lot less the time they are the furthest away from the nucleus
energy to escape to n = . and held less strongly.
8 electrons (in 2p and 2s) require a lot more There are 8 electrons in the same lower main
energy than the 3 electrons at the higher energy level closer to the nucleus.
energy levels there is a big jump between
the three and these 8 electrons.
There is a gradual increase in I.E. in the 8 There is an increase in I.E. as electrons are
electrons removed from an increasingly positively charged
ion.
2 electrons (in 1s) need an even higher There are 2 electrons on an even lower energy
amount of ionization energy level; most of the time they are closer to the nucleus
than the other electrons and are held very tightly.

Write equations for the first 4 ionization energies of aluminium.

Sketch graphs showing successive ionization energies for Mg, Cl, F and Ca.

Study the table (from http://www.shodor.org/chemviz/ionization/students/background.htm ) below

showing the first seven ionization energies for the first 12 elements.

How do the successive ionization energies show what group an element belongs to?

ionization energies in kJ/mol

1 2 3 4 5 6 7 8
H 1312
He 2372 5250
Li 520 7297 11810
Be 899 1757 14845 21000
B 800 2426 3659 25020 32820
C 1086 2352 4619 6221 37820 47260
N 1402 2855 4576 7473 9442 53250 64340
O 1314 3388 5296 7467 10987 13320 71320 84070
F 1680 3375 6045 8408 11020 15160 17860 92010
Ne 2080 3963 6130 9361 12180 15240
Na 496 4563 6913 9541 13350 16600 20113 25666
Mg 737 1450 7731 10545 13627 17995 21700 25662

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