1.1.9

Specific Impacts on Ionisation Energies

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Impact of Sub-Shell Structure on Ionisation Energy

The impact of the sub-shell structure is enough to sometimes outweigh and contrast general trends in ionisation energy.

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Example of sub-shell impact

  • An example of the impact of the sub-shell structure is the difference in ionisation energies between magnesium and aluminium within Period 3.
    • They are in the same period and so we would expect aluminium's ionisation energy to be greater due to a greater nuclear charge.
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Contrast to the trend

  • But the ionisation energies are:
    • Mg = 738 kJ/mol.
    • Al = 578 kJ/mol.
  • These values do not align with the general trend we predicted.
    • We need to look at the sub-shell structure of these atoms to understand what is going on.
Illustrative background for Mg vs Al sub-shell structureIllustrative background for Mg vs Al sub-shell structure ?? "content

Mg vs Al sub-shell structure

  • Mg = 1s22s22p63s2
    • So the first ionisation removes an electron from the 3s orbital.
  • Al = 1s22s22p63s23p1
    • So the first ionisation removes an electron from the 3p orbital.
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Sub-shell energies

  • The 3p orbital is further from the nucleus on average than the 3s orbital.
    • So this orbital has a higher energy and its electrons have a lower electrostatic attraction to the positive nucleus.
    • It is also slightly shielded by the 3s2 electrons.
  • So it's easier to ionise an electron in the 3p orbital than in the 3s orbital.
    • This explains why it is easier to ionise Al than Mg.
    • This effect outweighs the general trend we looked at first.
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Evidence

  • From these arguments, we can use the relative first ionisation energy values of Mg and Al as evidence for sub-shell structures.

Impact of Electron Repulsion on Ionisation Energy

The impact of electron repulsion can be seen in the ionisation energies of Group 5 and Group 6.

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Phosphorus and sulfur

  • Both P and S have their outer electron in a 3p orbital.
    • P = 1s22s22p63s23p3
    • S = 1s22s22p63s23p4
  • The shielding for each atom's outer electron is identical.
    • S has a higher nuclear charge and so you might expect S to have a higher ionisation energy. This is NOT the case.
Illustrative background for Singly vs doubly occupied orbitalsIllustrative background for Singly vs doubly occupied orbitals ?? "content

Singly vs doubly occupied orbitals

  • The P electron is removed from a singly occupied orbital but the S electron is removed from a doubly occupied orbital.
    • S has a lower ionisation energy because electrons in the same orbital repel each other.
    • This means that an electron is easier to remove from a doubly occupied orbital.
  • This gives more evidence for the electronic structure model we are using.

Jump to other topics

1Physical Chemistry

2Physical Chemistry 2 (A2 Only)

3Inorganic Chemistry

4Inorganic Chemistry 2 (A2 Only)

5Organic Chemistry 1

6Organic Chemistry 2 (A2 Only)

6.1Optical Isomerism (A2 Only)

6.2Aldehydes & Ketones (A2 Only)

6.3Carboxylic Acids & Esters (A2 Only)

6.4Aromatic Chemistry (A2 Only)

6.5Amines (A2 Only)

6.6Polymers (A2 Only)

6.7Biological Organic (A2 Only)

6.8Organic Synthesis (A2 Only)

6.9NMR Spectroscopy (A2 Only)

6.10Chromatography (A2 Only)

6.11A-A* (AO3/4) - Organic 2

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