1.1.9
Specific Impacts on Ionisation Energies
Impact of Sub-Shell Structure on Ionisation Energy
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.
Example of sub-shell impact
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.
Contrast to the trend
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.
Mg vs Al sub-shell structure
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.
Sub-shell energies
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.
Evidence
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
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.
Phosphorus and sulfur
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.
Singly vs doubly occupied orbitals
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.
1Physical Chemistry
1.1Atomic Structure
1.1.1Fundamental Particles
1.1.2Isotopes & Mass Number
1.1.3Mass Spectrometry
1.1.4Electron Shells, Sub-Shells & Orbitals
1.1.5Electron Configuration
1.1.6Ionisation Energy
1.1.7Factors Affecting Ionisation Energies
1.1.8Trends of Ionisation
1.1.9Specific Impacts on Ionisation Energies
1.1.10End of Topic Test - Atomic Structure
1.1.11A-A* (AO3/4) - Atomic Structure
1.2Amount of Substance
1.3Bonding
1.3.1Ionic Bonding
1.3.2Covalent & Dative Bonding
1.3.3Carbon Structures
1.3.4Metallic Bonding
1.3.5Physical Properties
1.3.6Shapes of Molecules
1.3.7Polarity
1.3.8Intermolecular Forces
1.3.9Intermolecular Forces 2
1.3.10End of Topic Test - Bonding
1.3.11Exam-Style Question - Shape of Molecules
1.3.12A-A* (AO3/4) - Bonding
1.4Energetics
1.5Kinetics
1.6Equilibria
2Physical Chemistry 2 (A2 Only)
2.1Thermodynamics (A2 Only)
2.2Rate Equations (A2 Only)
2.3The Equilibrium Constant Kp (A2 Only)
2.4Electrochemical Cells (A2 Only)
2.5Acids & Bases (A2 Only)
2.5.1Brønsted-Lowry Acids & Bases (A2 Only)
2.5.2pH (A2 Only)
2.5.3The Ionic Product of Water (A2 Only)
2.5.4Weak Acids & Bases (A2 Only)
2.5.5pH Curves & Titrations (A2 Only)
2.5.6pH Curves & Titrations 2 (A2 Only)
2.5.7Buffer Solutions (A2 Only)
2.5.8End of Topic Test - Acids & Bases
2.5.9Exam-Style Question - Weak Acids
2.5.10A-A* (AO3/4) - Acids & Bases
3Inorganic Chemistry
3.1Periodicity & Trends
4Inorganic Chemistry 2 (A2 Only)
4.1Period 3 (A2 Only)
4.2Transition Metals (A2 Only)
4.2.1General Properties (A2 Only)
4.2.2Substitution Reactions (A2 Only)
4.2.3Shapes of Complex Ions (A2 Only)
4.2.4Colours of Ions (A2 Only)
4.2.5Variable Oxidation States (A2 Only)
4.2.6Titrations (A2 Only)
4.2.7Homogeneous Catalysts (A2 Only)
4.2.8Heterogeneous Catalysts (A2 Only)
4.2.9End of Topic Test - Transition Metals
4.2.10A-A* (AO3/4) - Transition Metals
4.3Reactions of Ions in Aqueous Solutions (A2 Only)
5Organic Chemistry 1
5.1Introduction
5.2Alkanes
5.3Halogenoalkanes
5.4Alkenes
5.5Alcohols
5.6Organic Analysis
5.7A-A* (AO3/4) - Organic 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
Jump to other topics
1Physical Chemistry
1.1Atomic Structure
1.1.1Fundamental Particles
1.1.2Isotopes & Mass Number
1.1.3Mass Spectrometry
1.1.4Electron Shells, Sub-Shells & Orbitals
1.1.5Electron Configuration
1.1.6Ionisation Energy
1.1.7Factors Affecting Ionisation Energies
1.1.8Trends of Ionisation
1.1.9Specific Impacts on Ionisation Energies
1.1.10End of Topic Test - Atomic Structure
1.1.11A-A* (AO3/4) - Atomic Structure
1.2Amount of Substance
1.3Bonding
1.3.1Ionic Bonding
1.3.2Covalent & Dative Bonding
1.3.3Carbon Structures
1.3.4Metallic Bonding
1.3.5Physical Properties
1.3.6Shapes of Molecules
1.3.7Polarity
1.3.8Intermolecular Forces
1.3.9Intermolecular Forces 2
1.3.10End of Topic Test - Bonding
1.3.11Exam-Style Question - Shape of Molecules
1.3.12A-A* (AO3/4) - Bonding
1.4Energetics
1.5Kinetics
1.6Equilibria
2Physical Chemistry 2 (A2 Only)
2.1Thermodynamics (A2 Only)
2.2Rate Equations (A2 Only)
2.3The Equilibrium Constant Kp (A2 Only)
2.4Electrochemical Cells (A2 Only)
2.5Acids & Bases (A2 Only)
2.5.1Brønsted-Lowry Acids & Bases (A2 Only)
2.5.2pH (A2 Only)
2.5.3The Ionic Product of Water (A2 Only)
2.5.4Weak Acids & Bases (A2 Only)
2.5.5pH Curves & Titrations (A2 Only)
2.5.6pH Curves & Titrations 2 (A2 Only)
2.5.7Buffer Solutions (A2 Only)
2.5.8End of Topic Test - Acids & Bases
2.5.9Exam-Style Question - Weak Acids
2.5.10A-A* (AO3/4) - Acids & Bases
3Inorganic Chemistry
3.1Periodicity & Trends
4Inorganic Chemistry 2 (A2 Only)
4.1Period 3 (A2 Only)
4.2Transition Metals (A2 Only)
4.2.1General Properties (A2 Only)
4.2.2Substitution Reactions (A2 Only)
4.2.3Shapes of Complex Ions (A2 Only)
4.2.4Colours of Ions (A2 Only)
4.2.5Variable Oxidation States (A2 Only)
4.2.6Titrations (A2 Only)
4.2.7Homogeneous Catalysts (A2 Only)
4.2.8Heterogeneous Catalysts (A2 Only)
4.2.9End of Topic Test - Transition Metals
4.2.10A-A* (AO3/4) - Transition Metals
4.3Reactions of Ions in Aqueous Solutions (A2 Only)
5Organic Chemistry 1
5.1Introduction
5.2Alkanes
5.3Halogenoalkanes
5.4Alkenes
5.5Alcohols
5.6Organic Analysis
5.7A-A* (AO3/4) - Organic 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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