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Giant Covalent Structures

A concise revision guide to giant covalent structures: how diamond, graphite and graphene are bonded, why their properties differ so much, and how the structure explains melting point, hardness and electrical conductivity.

Paper 1 and 2
2.2.2: Bonding and Structure
H432/01 and H432/02
Dr. Mohammed Al-Fatah

Written by:
Dr. Mohammed Al-Fatah

Chemistry specialist revision notes for A Level Chemistry.

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Before you start

GCSE Recap: Covalent Bonds and Small Molecules

Before you start, check three GCSE ideas that this page builds on.

1

What Is a Giant Covalent Structure?

In a giant covalent structure (also called a macromolecular or giant molecular structure) every atom is joined to its neighbours by strong covalent bonds that extend throughout the whole crystal. There are no separate molecules: a single crystal of diamond is, in effect, one enormous molecule. Compare this with a simple molecular substance such as iodine, where strong covalent bonds hold each I2 molecule together but only weak intermolecular forces act between the molecules.

FeatureGiant covalent (diamond, graphite, graphene)Simple molecular (iodine, ice, carbon dioxide)
ParticlesAtoms in a continuous networkDiscrete molecules
Forces broken on meltingStrong covalent bondsWeak intermolecular forces
Melting pointVery high (diamond sublimes above 3600 °C)Low
Solubility in waterInsolubleUsually low; some polar molecules dissolve
Electrical conductivityUsually none; graphite and graphene conductNone

Key idea: Melting a giant covalent structure means breaking covalent bonds, which needs a great deal of energy, so these substances have very high melting points and are hard or, in the case of graphite, strongly bonded within each layer.

Check your understanding

Quick Check: Identify the Structure from Data

Use the data to decide which type of structure the solid has.

2

Diamond

In diamond each carbon atom forms four single covalent bonds to four other carbon atoms arranged tetrahedrally around it, with bond angles of 109.5°. The result is a rigid three-dimensional network in which every atom is locked in place by strong C-C bonds.

PropertyExplanation from the structure
Very high melting and sublimation pointMany strong covalent bonds must be broken
Extremely hardThe rigid tetrahedral network resists any distortion; diamond is used in cutting tools and drill tips
Does not conduct electricityAll four outer electrons of each carbon are used in bonding, so there are no delocalised electrons
Insoluble in all solventsNo solvent interaction can compete with the covalent bonds

Silicon has the same structure as diamond, which is why it is also a hard, high-melting solid, although its Si-Si bonds are weaker than C-C bonds. Silicon atoms are larger than carbon atoms, so the Si-Si bond is longer and the shared pair is further from both nuclei. This is why silicon melts at a lower temperature than diamond.

Exam sentence: Diamond has a giant covalent structure in which each carbon atom is bonded to four others by strong covalent bonds, so a large amount of energy is needed to break the bonds and it has a very high melting point.

Check your understanding

Quick Check: Predict the Properties of Silicon Carbide

Use the structure described to predict the properties of a compound you have not met on this page.

Check your understanding

Quick Check: Explain Silicon and Phosphorus

Write a short explanation, then compare it with the mark points and the model answer.

3

Graphite

In graphite each carbon atom forms three covalent bonds to three other carbon atoms, giving flat hexagonal layers with bond angles of 120°. The fourth outer electron of each carbon is not used in a localised bond; it sits in a p orbital above and below the layer and becomes delocalised across the whole sheet. The layers are held to each other only by weak induced dipole-dipole interactions (London forces), and are relatively far apart.

PropertyExplanation from the structure
Very high melting pointThe strong covalent bonds within the layers must be broken
Soft and slipperyThe weak forces between layers let them slide over each other; graphite is used as a lubricant and in pencils
Conducts electricityThe delocalised electrons can move along the layers when a voltage is applied. Graphite conducts well along the layers but very poorly at right angles to them, because the electrons cannot move easily from one layer to the next
Low density compared with diamondThe layers are widely spaced
InsolubleCovalent bonding throughout the layers

Exam focus: Graphite conducts because it has delocalised electrons; it is soft because the layers are held together only by weak induced dipole-dipole interactions (London forces). Do not say the layers are held by covalent bonds, and do not say graphite conducts because it is a metal.

Check your understanding

Quick Check: Which Way Does Graphite Conduct?

Predict what happens when the conductivity of a graphite crystal is measured in two directions.

4

Graphene

Graphene is a single layer of graphite: a sheet of carbon atoms one atom thick, each bonded covalently to three others in a hexagonal pattern, with one delocalised electron per carbon spread over the sheet. It is described as a two-dimensional giant covalent structure.

PropertyExplanationApplication
Extremely strong for its thicknessStrong covalent bonds throughout the sheetReinforcing composites and lightweight materials
Excellent electrical conductorDelocalised electrons move freely across the sheetFlexible electronics, touchscreens, sensors
Very good thermal conductorVibrations pass easily through the rigid covalent networkHeat management in electronic devices
Transparent and flexibleA single atomic layer absorbs little light and can bend without breaking bondsTransparent conducting films

Giant Covalent Structures: Diamond, Graphite, Graphene and SiO2

Start from one atom and its bonds, build the network outwards, and see how the bonding in each structure explains its properties.

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Carbon Silicon Oxygen Covalent bond Delocalised electrons Bond angle Unit outline

© Dr. Mohammed Al-Fatah – onlinelearningsystem.net

Exam sentence: Graphene is a single layer of graphite in which each carbon atom is covalently bonded to three others; the delocalised electrons make it an excellent conductor and the covalent network makes it very strong.

Check your understanding

Quick Check: From Graphene to Nanotubes

Apply what you know about graphene to two related materials, answering each question as quickly as you can.

5

Comparing the Three Carbon Structures

DiamondGraphiteGraphene
Bonds per carbon atom433
ArrangementTetrahedral, 109.5°, three-dimensionalHexagonal layers, 120°One hexagonal layer, 120°
Delocalised electronsNoneOne per carbon, within each layerOne per carbon, across the sheet
Electrical conductivityNoneAlong the layersExcellent
HardnessExtremely hardSoft, layers slideVery strong sheet
Melting pointVery highVery highVery high

Key idea: The same element gives three very different materials because the bonding arrangement differs: four localised bonds give hardness and no conduction; three bonds plus a delocalised electron give layers that conduct.

Check your understanding

Quick Check: Two Forms of Boron Nitride

Drag the words into place to compare the two forms of another giant covalent substance.

6

Where This Sits in the OCR Specification

OCR A places the giant covalent lattices of carbon (graphene, graphite, diamond) and silicon in section 3.1.1 Periodicity, where they are contrasted with the giant metallic lattices of the Period 3 metals. The bonding ideas belong here in 2.2.2, so this page is included with the covalent bonding notes; expect the exam question to appear in a periodicity context and to ask about silicon as well as carbon.

7

Common Exam Mistakes

  • Saying graphite is soft because its covalent bonds are weak. The covalent bonds are strong; it is the forces between layers that are weak.
  • Saying diamond conducts electricity, or that graphite conducts because it contains ions or is metallic. Only delocalised electrons explain the conduction.
  • Describing melting as breaking intermolecular forces. In a giant covalent structure the covalent bonds themselves must be broken.
  • Forgetting the bond angle: 109.5° in diamond, 120° in graphite and graphene.
  • Drawing a diamond fragment with carbon atoms that have only three bonds, or a graphite layer with four bonds per carbon.

Exam sentence: Giant covalent structures have very high melting points because many strong covalent bonds must be broken; only those with delocalised electrons, graphite and graphene, conduct electricity.

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Copyright and author footprint: This OLS revision page was written for Online Learning System by Dr. Mohammed Al-Fatah. It is designed for A Level Chemistry revision and should not be copied or redistributed without permission.