S2.2Structure 2 — Models of bonding and structure
The covalent model — IB Chemistry SL Revision Notes & Topical Questions
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Lesson summary
S2.2 The covalent model — IB CHEMISTRY SL notes: Draw Lewis formulas, deduce shapes and polarity, describe giant covalent structures, link intermolecular forces to properties and interpret chromatography.Covalent bond = the electrostatic attraction between a shared pair of electr…
- Occurrence
- Orbital overlap
- Octet rule
- Exceptions
- Multiple bonds
- Representations
Part 1 of 10Covalent bonding
Covalent bond
Covalent bond the electrostatic attraction between a shared pair of electrons and the nuclei of the two bonded atoms.
Occurrence
- Occurrence between two non-metals, with electrons shared rather than transferred.
Orbital overlap
- Orbital overlap two atomic orbitals overlap to form a molecular orbital, and sharing is more stable than holding electrons on one atom.
Octet rule
- Octet rule atoms share electrons to gain a noble-gas valence shell of eight electrons.
- (a duet for hydrogen)
Exceptions
- Be in BeCl2 has 4 electrons around it and B in BF3 has 6, and these molecules are stable.
Multiple bonds
- Multiple bonds single, double and triple bonds share 2, 4 and 6 electrons, and quadruple bonds are impossible because repulsion is too great.
Part 2 of 10Drawing Lewis formulas
1
Count the total valence electrons, adding one per negative charge and subtracting one per positive charge.
2
Draw the skeleton with the least electronegative atom central (never hydrogen), joined by single bonds.
3
Complete the octets of outer atoms with lone pairs, then place any remaining electrons on the central atom.
4
If the central atom lacks an octet, convert lone pairs on outer atoms into double or triple bonds.
5
Check that all valence electrons are used and every atom has an octet (a duet for H).
Lewis formula
- Lewis formula shows all valence electrons as bonding pairs and lone pairs, so Cl–Cl alone is not a Lewis formula.
Representations
- Representations a pair can be dots, crosses, a mixture of both, or a line.
Part 3 of 10Bond length and strength; coordinate bonds
Bond strength
- Bond strength triple > double > single, because more shared electrons pull the nuclei closer.
Bond length
- Bond length single > double > triple, e.g. C–C 154 pm, C=C 134 pm and C≡C 120 pm.
Bond energy
- Bond energy the energy needed to break one mole of a bond in the gaseous state, in kJ mol−1.
Coordinate bond
Coordinate bond a covalent bond in which both electrons come from the same atom.
Formation
- Formation a lone pair is donated into an empty orbital, e.g. NH3 + H+ → NH4+.
- Identical bonds — once formed it is the same as other covalent bonds, so all four N–H bonds in NH4+ are identical.
- Electron-deficient acceptor — BF3 can accept a lone pair, e.g. forming F3B–NH3.
Part 4 of 10VSEPR shapes
Principle
- Principle electron domains repel and spread as far apart as possible.
- (bonding pairs, lone pairs, each multiple bond counting as one)
Repulsion order
- Repulsion order lone pair–lone pair > lone pair–bonding pair > bonding pair–bonding pair.
| Domains | Bonding | Lone pairs | Molecular shape | Angle | Example |
|---|---|---|---|---|---|
| 2 | 2 | 0 | Linear | 180° | CO2 |
| 3 | 3 | 0 | Trigonal planar | 120° | BF3 |
| 3 | 2 | 1 | Bent | about 118° | SO2 |
| 4 | 4 | 0 | Tetrahedral | 109.5° | CH4 |
| 4 | 3 | 1 | Trigonal pyramidal | 107° | NH3 |
| 4 | 2 | 2 | Bent | 104.5° | H2O |
1Domain geometry versus molecular shape
- Domain geometry versus molecular shape they can differ, e.g. NH3 has tetrahedral domains but a trigonal pyramidal shape.
2Lone pairs
- Lone pairs each reduces the bond angle by about 2–2.5°.
Part 5 of 10Bond polarity and molecular polarity
1Electronegativity
Electronegativity the ability of an atom to attract the shared pair in a bond, on the Pauling scale (F is highest at 4.0).
2Polar bond
- Polar bond unequal sharing gives δ+ on the less electronegative atom and δ− on the other, and a larger difference means a more polar bond.
3Non-polar bond
- Non-polar bond identical atoms such as H2 and Cl2 share equally.
4Non-polar molecule with polar bonds
- Non-polar molecule with polar bonds symmetrical geometry cancels the dipoles, as in CO2 and CCl4.
5Polar molecule
- Polar molecule asymmetrical geometry leaves a net dipole, as in H2O, NH3 and CHCl3.
6Rule
- Rule a molecule with only non-polar bonds cannot be polar.
Part 6 of 10Giant covalent structures
| Substance | Structure | Conductivity | Properties |
|---|---|---|---|
| Diamond | Each C bonded tetrahedrally to 4 others | None | Very hard, very high melting point |
| Graphite | Each C bonded to 3 in hexagonal layers; layers held by London forces | Conducts along layers (one delocalised electron per atom) | Soft and slippery |
| Graphene | A single layer of graphite | Excellent | Strong, flexible and one atom thick |
| C60 fullerene | Discrete spherical molecules with 20 hexagons and 12 pentagons | Poor (semiconductor) | Low melting point; not a giant structure |
| Silicon | Diamond-like network | Poor | High melting point |
| Silicon dioxide | Each Si bonded to 4 O and each O to 2 Si, formula SiO2 | None | High melting point, hard, insoluble |
- Melting points
- covalent bonds, not intermolecular forces, must break in network solids.
Part 7 of 10Intermolecular forces
1Intermolecular forces
- Intermolecular forces act between molecules and are much weaker than covalent bonds, which are intramolecular.
2London (dispersion) forces
- London (dispersion) forces arise from instantaneous dipoles inducing dipoles in neighbours, are present in all substances and grow with more electrons and greater surface area.
3Dipole-induced dipole
- Dipole-induced dipole a permanent dipole distorts the electron cloud of a non-polar neighbour.
4Dipole-dipole
- Dipole-dipole attraction between the δ+ and δ− ends of polar molecules.
5Hydrogen bonding
- H bonded to N, O or F is attracted to a lone pair on N, O or F in a neighbouring molecule, the strongest of these forces.
6Strength order
- London < dipole-dipole < hydrogen bonding for similar molar mass.
7Branching
- Branching straight-chain alkanes have higher boiling points than branched isomers.
8Hydrogen bonding examples
- Hydrogen bonding examples the anomalously high boiling points of H2O, HF and NH3, and ice being less dense than water.
Part 8 of 10Properties of molecular substances
Properties of molecular substances
Melting and boiling points
- Melting and boiling points depend on the strength of intermolecular forces, and low boiling points mean volatile.
Solubility
- "like dissolves like", so polar and hydrogen-bonding solutes dissolve in water and non-polar solutes in non-polar solvents such as hexane.
Conductivity
- Conductivity molecular substances have no mobile charged particles, so they do not conduct, except graphite and graphene.
Polar molecules that ionise
- Polar molecules that ionise such as HCl conduct in solution because ions form.
Small alcohols
- Small alcohols ethanol dissolves in water, but solubility falls as the hydrocarbon chain lengthens.
Part 9 of 10Paper chromatography and R<sub>f</sub>
1
Draw a pencil baseline about 1 cm from the bottom of the paper.
2
Spot the samples on the baseline and let them dry.
3
Stand the paper in solvent with the level below the baseline and cover to saturate the atmosphere.
4
Remove the paper when the solvent is near the top and mark the solvent front immediately.
5
Locate colourless spots with a UV lamp or a locating agent such as ninhydrin.
6
Measure distances from the baseline and calculate Rf.
Rf
Rf distance moved by the spot ÷ distance moved by the solvent front, both from the baseline.
Properties of Rf
- Properties of Rf it has no unit and lies between 0 and 1.
Interpretation
- Interpretation components more soluble in the solvent and less attracted to the stationary phase travel further and have a higher Rf;
- compare with references run under identical conditions.
Part 10 of 10More from the specification
More from the specification
Covalent bond nature
- Electrostatic attraction between a shared pair of valence electrons and two positively charged atomic nuclei.
Polar vs nonpolar molecules
- Symmetrical charge distribution produces nonpolar molecules with dispersion forces only;
- asymmetrical distribution yields permanent dipole moments.
Electrical conductivity limitations
- Simple covalent molecular substances do not conduct electricity in any state because they lack mobile charged particles.
- (ions or delocalised electrons)
Physical properties of simple molecules
- Low melting and boiling points due to weak intermolecular forces operating between intact covalent molecules.
Physical property
- A property observed or measured without changing the material.
Key terms
| Term | Meaning |
|---|---|
| Covalent bond | The attraction between a shared pair of electrons and the two nuclei. |
| Coordinate bond | A covalent bond in which both electrons come from the same atom. |
| VSEPR theory | Electron domains around a central atom repel to be as far apart as possible, with lone pairs repelling most. |
| Electronegativity | The ability of an atom to attract the shared pair in a covalent bond. |
| Allotropes | Different structural forms of the same element in the same state. |
| London (dispersion) forces | Weak attractions between instantaneous and induced dipoles. |
| Hydrogen bond | Attraction between H bonded to N, O or F and a lone pair on N, O or F of another molecule. |
Avoid these mistakes
1
Saying covalent molecules melt by breaking covalent bonds — only intermolecular forces are overcome (except in network solids).
2
Assuming polar bonds always make a polar molecule — symmetrical shapes such as CO2 cancel the dipoles.
3
Forgetting lone pairs when predicting shape — draw the Lewis formula first.
4
Quoting Rf with units or values above 1 — it is a ratio less than 1.
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