Module 2 Foundations in chemistry

Chapter 6 Shapes of molecules and intermolecular forces

6.1 Shapes of molecules and ions

Electron pair repulsion theory

An electron has a negative charge, so electron pairs repel one another. The electron-pair repulsion
theory is a model used to explain and predict the shapes of molecules and polyatomic ions.

 Electron pairs surrounding a central atom and the number of electron pairs determine the
shape of the molecule or ion.
 Electrons pairs repel one another as far apart as possible.
 Arrangement of electrons pairs minimises repulsion and so holds the bonded atoms in a
definite shape.

Shapes of molecules

Representing molecules in 3D – wedges

 A solid line represents a bond in the plane of the paper.

 A solid wedge comes out of the plane of the paper.
 A dotted wedge goes into the plane of the paper.

Bonded-pair and lone-pair repulsions

A lone pair of electrons is slightly closer to the central atoms and occupies more space than a
bonded pair, so a lone pair repels more strongly than a bonding pair.

Molecular shapes from 4 electron pairs

 4 electron pairs around the central atom repel

one another as far apart as possible into a
tetrahedral shape.
 Lone pairs repel more strongly than bonded
pairs. So, decreases the bond angle by 2.5° for
each lone pair.

Molecular shapes with multiple bonds

In molecules with multiple bonds, each multiple bond is treated as a bonding region.

Molecular shapes from other number of electron pairs

The principal of electron-pair repulsion theory can be applied to any number of electron pairs
surrounding the central atom.

Remember that dot-and-cross diagram can be very useful for working out the arrangement of
electron pairs and molecular shapes. Always draw the dot-and-cross diagram to help.

Molecular shape rules

1. A single bond counts as 1 bonding pair.

2. A double or triple bond count as 1 region of electron density (this counts the same as a
bonding pair).
3. Bonding pairs repel each other as far apart as possible equally.
4. Lone pairs count as a region of electron density, but repel more, decreasing the bond angle
by 2.5°.

6.2 Electronegativity and polarity

Electronegativity a measure of the attraction of a bonded tom for the pair of electrons in a covalent
bond.
In a covalent bond, the nuclei of the bonded atoms attract the shared pair of electrons. In molecules
of elements e.g. H2, O2, N2, and Cl2 the atoms are the same element and the bonded electron pair is
shared evenly.

This changes when the bonded atoms are different elements:

 Nuclear charges are different.

 Atoms may be different sizes.
 Shared pair of electrons may be closer to one nucleus than the other.

The shared pair of electrons in the covalent bond may experience more attraction from one of the
bonded atoms than the other.

How is electronegativity measured?

The Pauling scale is used to compare the electronegativity of the atoms

of different elements. Pauling electronegativity values depend on the
element’s position in the periodic table.

Across the periodic table

 Nuclear charge increases.

 Atomic radius decreases.

A large Pauling value shows that atoms of the element are very
electronegative. Electronegativity increases across and up the periodic table, so fluorine the most
electronegative atom. The noble gases are not included as they tend NOT to form compounds.

 Non-metals nitrogen, oxygen, fluorine and chlorine have the most electronegative atoms.
 Group 1 metals have the least electronegative atoms (Li, Na, K, RB, Cs and Fr).

Ionic or covalent?

If the electronegativity difference is large, one bonded atom will have a greater
attraction for the shared pair than the other bonded atom. The more
electronegative atom will have gained control of the electrons and the bond will
now be ionic rather than covalent.

Bond polarity

Non-polar bonds – no charge separation across bond.

In a non-polar bond, the bonded electron pair is shared equally between the bonded atoms. A bond
will be non-polar when:

 Bonded atoms are the same or

 Bonded atoms have the same or similar electronegativity.

In molecules of elements e.g. hydrogen, oxygen and chlorine the bonded atoms
come from the same element and the electron pair is shared equally. The bond is
a pure covalent bond. Carbon and hydrogen are electronegativities and form non-polar bonds.
Hydrocarbon liquids e.g. hexane are non-polar solvents and do not mix with water.

Polar bonds

In a polar bond, the bonded electron pair is shared unequally between the bonded atoms. A bond
will be polar when bonded atoms are:

 Different
 Have different electronegativity values.

Resulting in a polar covalent bond.

E.g. Hydrogen chloride

Hydrogen chloride has atoms of different elements.

 Hydrogen has an electronegativity of 2.1 and chlorine has an electronegativity of 3.

 Chlorine atom is more electronegative than the hydrogen atom.
 Chlorine atom has a greater attraction for the bonded pair of electrons than the hydrogen
atom, resulting in a polar covalent bond.

The H—Cl bond is polarised with a small partial positive charge (δ+) on the
hydrogen atom and a small partial negative charge (δ-) on the chlorine atom.

Delta symbol δ means small

δ+ and δ- are partial charges and are much smaller than a full + and – charge.

 This separation of charges is called a dipole.

 The hydrogen chlorine molecule is polar with δ+ and δ- charges at different ends of the H
—Cl bond.

A dipole in a polar covalent bond does NOT change and is called a permanent dipole to distinguish it
from an induced dipole.

If you are provided with Pauling electronegativity values:

 Atom with larger electronegativity has δ− charge.

 Atom with smaller electronegativity has δ+ charge.

Polar molecules

Hydrogen chloride is a polar molecule as the H—Cl bond has one permanent dipole acting in the
direction of the H—Cl bond. For molecules with more than 2 atoms, there may be 2 or more polar
bonds. Depending on the shape of the molecule, the dipoles may reinforce one another to produce a
larger dipole over the whole molecule or cancel out if the dipoles act in opposite directions.

A water molecule (H2O) is polar.

 Two O—H bonds each have a permanent dipole.

  The two dipoles act in different direction but do not exactly oppose one another.
 Overall the oxygen end of the molecule has a δ- charge and the hydrogen end has a δ+
charge.

A carbon dioxide molecule is non-polar (CO2).

 Two C=O bonds each have a permanent dipole.

 The two dipoles act in opposite directions and exactly oppose one
another.
 Over the whole molecule, the dipoles cancel and the overall dipole is
zero.

Polar solvents and solubility

Sodium chloride lattice is being dissolved by water molecules to form aqueous

sodium and chloride ions:

NaCl (s) + aq  Na+ (aq) + Cl- (aq)

 Water molecules attract Na+ and Cl- ions.

 The ionic lattice breaks down as it dissolves.
 In the resulting solution, water molecules surround the Na + and Cl-
ions.
 Na+ ions are attracted towards the oxygen of water molecules (δ-)
 Cl- ions are attracted towards the hydrogen of water molecules (δ-)

Polar molecules are non-symmetrical.

Non-polar molecules are symmetrical.

6.3 Intermolecular forces

Forces between molecules

Covalent bonding is strong and holds the atoms in a molecule together.

Intermolecular forces are weak interactions between dipoles of different molecules. Types of
intermolecular forces:

 Induced dipole-dipole interactions

(London forces)
 Permanent dipole-dipole interactions
 Hydrogen bonding

Induced dipole-dipole interactions

London forces are weak intermolecular forces that exist between ALL molecules. They act between
induced dipoles in different molecules. Induced dipoles are temporary.

The strength of induced dipole-dipole interactions (London forces)

Induced dipoles result from interactions of electrons between molecules. The more electrons in each
molecule:

 The larger the instantaneous and induced dipoles

 The greater the induced dipole-dipole interactions
 The stronger the attractive forces between molecules.

Larger numbers of electrons = larger induced dipoles, so more energy is needed to overcome the
intermolecular forces, increasing the boiling point.

Permanent
dipole-dipole
interactions
Permanent dipole-dipole interactions act between the permanent dipoles in different polar
molecules.

Polar molecules have induced dipole-dipole interactions as well as permanent dipole-dipole

interactions.

 Fluorine molecules are non-polar and only have London forces. Hydrogen chloride molecules
are polar and have London forces and permanent dipole-dipole interactions.
 Extra energy is needed to break the additional permanent dipole-dipole interactions
between hydrogen chloride molecules.
 So, the boiling point of hydrogen chloride is higher than fluorine.

Simple molecular substances

A simple molecular substance is made up of simple molecules – small units containing

a definite number of atoms with a definite molecular formula e.g. Ne, H 2, H2O and CO2.

In the solid state, simple molecules form a regular structure called a simple molecular
lattice:

 Molecules held in place by WEAK intermolecular forces.

 Atoms within each molecule are bonded by STRONG covalent bonds.

Properties of simple molecular substances

Low melting and boiling points

All simple molecular substances are covalently bonded.

 Weak intermolecular forces in the simple molecular lattice can be broken by energy present
as low temperatures.

When a simple molecular lattice is broken during melting, only weak intermolecular forces break,
the covalent bonds are strong and so do not break.

Electrical conductivity

 No mobile charged particles, nothing to complete electrical circuit.

 Does NOT conduct electricity.

Solubility
Covalent substances with simple molecular structures are either polar or non-polar.

Solubility of non-polar simple molecular Solubility of polar simple molecular substances

substances
When a NON-POLAR simple molecular
compound is added to a NON-POLAR solvent,
intermolecular forces form between the
molecules and solvent. The interactions weaken
the intermolecular forces in the simple
molecular lattice. The intermolecular forces
break and the compound dissolves.
Non-polar substance  soluble in non-polar
solvents.
Polar simple molecular substance may dissolve
in polar solvents as the polar solute and polar
solvent molecules can attract each other.
Solubility depends on the strength of the dipole
and can be hard to predict. E.g. ethanol
contains both polar (O-H) and non-polar
(carbon chain) parts in their structure and can
dissolve in both polar and non-polar solvents.

When a NON-POLAR simple molecular

compound is added to a POLAR solvent, there is
little interactions between the molecules in the
lattice and solvent. The intermolecular bonding
in the polar solvent is too strong to be broken.
Non-polar substance  insoluble in polar
solvents.

6.4 Hydrogen bonding

Hydrogen bonds

A hydrogen bond is a special type of permanent dipole-dipole interaction between molecules

containing:

 An electronegative atom with a lone pair of electrons e.g. O2, N2, F2

 A hydrogen atom attached to an electronegative atom e.g. H—O, H—N, H—F

The hydrogen bond acts between a lone pair of electrons on an electronegative atom in one
molecule and a hydrogen atom in a different molecule. Hydrogen bonds are the strongest type of
intermolecular interactions.

Hydrogen bond is shown by a dashed line. The shape around the hydrogen atom in the hydrogen
bond is linear.

Anomalous properties of water

Ice (solid) is less dense than water (liquid)

 2 lone pairs on oxygen and 2 hydrogen atoms, each water molecule can form 4
hydrogen bonds. They extend outwards holding water molecules apart in an
open lattice. This forms an open tetrahedral lattice full of holes. Bond angle
around the hydrogen atom in the bond is 180°.
 Water molecules in ice are further apart than in water.
 The holes decrease the density of water on freezing, so solid ice is less dense
than liquid water and floats.

As ice floats, in ponds and lakes it forms an insulating layer and prevents the water from
freezing solid – good for fish.

Water has a relatively high melting and boiling point

Water has London forces between molecules.

 Hydrogen bonds are extra forces on top of London forces.

 So more energy is needed to break the hydrogen bonds, so water has a much higher melting
and boiling point than expected from just London forces.
 When the ice lattice breaks, the rigid arrangement of hydrogen bonds in ice is broken. When
water boils, the hydrogen bonds break completely.

Relatively high surface tension and viscosity

Extra intermolecular bonding from hydrogen bonds mean that it has relatively high surface tension
and viscosity, this results in droplets that are ‘not wet’ and allow insects to walk on pond surfaces.
Detergents reduce the surface tension, making water ‘wetter’.