Covalent Bonding & Structure

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International AS Chemistry Edexcel 

1.7 Covalent Bonding & Structure

CONTENTS
1.7.1 Evidence of Covalent Bonding
1.7.2 Covalent Bonding
1.7.3 Carbon Allotropes
1.7.6 Predicting Shapes & Angles

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1.7.1 Evidence of Covalent Bonding YOUR NOTES



Evidence of Covalent Bonding
Covalent bonding occurs between two non-metals
A covalent bond involves the electrostatic attraction between nuclei of two atoms and
the electrons of their outer shells
No electrons are transferred but only shared in this type of bonding
When a covalent bond is formed, two atomic orbitals overlap and a molecular orbital is
formed
Covalent bonding happens because the electrons are more stable when attracted to two
nuclei than when attracted to only one

The positive nucleus of each atom has an attraction for the bonding electrons shared in the
covalent bond
In a normal covalent bond, each atom provide one of the electrons in the bond. A covalent
bond is represented by a short straight line between the two atoms, H-H
Covalent bonds should not be regarded as shared electron pairs in a fixed position; the
electrons are in a state of constant motion and are best regarded as charge clouds

A representation of electron charge clouds. The electrons can be found anywhere in the
charge clouds
Non-metals are able to share pairs of electrons to form different types of covalent bonds

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Sharing electrons in the covalent bond allows each of the 2 atoms to achieve an electron YOUR NOTES
configuration similar to a noble gas 
This makes each atom more stable
In some instances, the central atom of a covalently bonded molecule can accommodate
more or less than 8 electrons in its outer shell
Being able to accommodate more than 8 electrons in the outer shell is known as
‘expanding the octet rule’
Atoms from Period 3 and below can accommodate more than 8 electrons as the
d-orbitals are accessible
Common examples of elements that can have an 'expanded octet' are
phosphorous and sulfur
For example, PCl5, which has 10 electrons around the central phosphorus atom
In SF6, there are 12 electrons around the central sulfur atom
Accommodating less than 8 electrons in the outer shell means that the central atom is
‘electron deficient’
Boron has 3 electrons in its outer shell, 2s22p1
When it forms a covalent compound, these three electrons are paired
For example, BF3 which has 6 electrons around the central boron atom
Covalent bonding & simple covalent lattice structures
Covalent bonding can be responsible for substances that have many different structures
and therefore different physical properties
Small molecules such as H2O and N2 are simple units made from covalently bonded atoms
These simple molecules contain fixed numbers of atoms
Simple covalent lattices have low melting and boiling points
These compounds have weak intermolecular forces between the molecules
Only little energy is required to break the lattice
Most compounds are insoluble with water
Unless they are polar and can form hydrogen bonds (such as sucrose)
They do not conduct electricity in the solid or liquid state as there are no charged particles
Some simple covalent compounds do conduct electricity in solution, but this is
because their interaction with water produces ions, for example, HCl which forms H+
and Cl- ions when in aqueous solution
Buckminsterfullere, C60, is an exception to some of these general points about simple
molecules
Buckminsterfullerene and other fullerenes are spherical networks of carbon atoms
They are made up of large molecules but they are not classed as giant covalent
structures
Compared to other simple covalent molecules, buckminsterfullerene has a higher
melting and boiling point
Fullerenes are generally larger molecules so will have larger intermolecular forces
because of the number of electrons within the molecule which require more
energy to overcome
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Fullerenes are good insulators as, despite having delocalised electrons within their YOUR NOTES
structure, these cannot pass between molecules and therefore cannot conduct 
electricity
Covalent bonding & giant covalent lattice structures
Giant covalent structures have a huge number of non-metal atoms bonded to other non-
metal atoms via strong covalent bonds
These structures can also be called giant lattices and have a fixed ratio of atoms in the
overall structure
Some of the common macromolecules you should know about include diamond and
graphite
Giant covalent lattices have very high melting and boiling points
These compounds have a large number of covalent bonds linking the whole structure
A lot of energy is required to break the lattice
The compounds can be hard or soft
Graphite is soft as the forces between the carbon layers are weak
Diamond and silicon(IV) oxide are hard as it is difficult to break their 3D network of
strong covalent bonds
Most compounds are insoluble with water
Most compounds do not conduct electricity however some do
In graphite, each carbon atom has three outer electrons that are involved in bonding to
other carbon atoms, leaving one electron which becomes delocalised between the
carbon layers and can move along the layers when a voltage is applied
Diamond and silicon(IV) oxide do not conduct electricity as all four outer electrons on
every carbon atom are involved in a covalent bond so there are no freely moving
electrons available

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1.7.2 Covalent Bonding YOUR NOTES



Covalent Dot & Cross Diagrams
Covalent compounds
The atoms in covalent compounds will share their outer valence electrons to achieve
a noble gas configuration

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YOUR NOTES

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Dot-and-cross diagrams of covalent compounds in which the atoms share their valence
electrons
Double covalent bonding
Oxygen, O2

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Covalent bonding in oxygen


Carbon dioxide, CO2

Covalent bonding in carbon dioxide


Ethene, C2H4

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Covalent bonding in ethene


Triple covalent bonding
Nitrogen, N2

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Covalent bonding in nitrogen YOUR NOTES


Dative covalent bonding 
In simple covalent bonds, the two atoms involved share electrons
Some molecules have a lone pair of electrons that can be donated to form a bond with
an electron-deficient atom
An electron-deficient atom is an atom that has an unfilled outer orbital
So both electrons are from the same atom
This type of bonding is called dative covalent bonding or coordinate bonding
An example with a dative bond is in an ammonium ion
The hydrogen ion, H+ is electron-deficient and has space for two electrons in its shell
The nitrogen atom in ammonia has a lone pair of electrons which it can donate to the
hydrogen ion to form a dative covalent bond

Ammonia (NH3) can donate a lone pair to an electron-deficient proton (H+) to form a
charged ammonium ion (NH4+)

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Aluminium chloride YOUR NOTES


Aluminium chloride is also formed using dative covalent bonding 
At high temperatures aluminium chloride can exist as a monomer (AlCl3)
The molecule is electron-deficient and needs two electrons to complete the
aluminium atom’s outer shell
At lower temperatures the two molecules of AlCl3 join together to form a dimer (Al2Cl6)
The molecules combine because lone pairs of electrons on two of the chlorine atoms
form two coordinate bonds with the aluminium atoms

Aluminium chloride is also formed with a dative covalent bond in which two of the chlorine
atoms donate their lone pairs to each of the aluminium atoms to form a dimer

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Exam Tip YOUR NOTES


 Covalent bonding takes place between nonmetal atoms.

Remember: Use the Periodic Table to decide how many electrons are in the outer
shell of a nonmetal atom.

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1.7.3 Carbon Allotropes YOUR NOTES



Carbon Allotropes
Covalent bonding & giant covalent lattice structures
Allotropes of carbon are substances contain only carbon atoms but due to the differences
in bonding arrangements they are physically completely different
Giant covalent lattices have very high melting and boiling points
These compounds have a large number of covalent bonds linking the whole structure
A lot of energy is required to break the lattice
The compounds can be hard or soft
Graphite is soft as the forces between the carbon layers are weak
Diamond and silicon(IV) oxide are hard as it is difficult to break their 3D network of
strong covalent bonds
Most compounds are insoluble with water
Most compounds do not conduct electricity however some do
Graphite has delocalised electrons between the carbon layers which can move along
the layers when a voltage is applied
Diamond and silicon(IV) oxide do not conduct electricity as all four outer electrons on
every carbon atom are involved in a covalent bond so there are no freely moving
electrons available
Graphite
Each carbon atom in graphite is bonded to three others forming layers of hexagons,
leaving one free electron per carbon atom
These free electrons migrate along the layers and are free to move and carry charge, hence
graphite can conduct electricity
The covalent bonds within the layers are very strong, but the layers are attracted to each
other by weak intermolecular forces, so the layers can slide over each other making
graphite soft and slippery

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Diagram showing the structure and bonding arrangement in graphite


Diamond
In diamond, each carbon atom bonds with four other carbons, forming a tetrahedron
All the covalent bonds are identical, very strong and there are no intermolecular forces

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Diagram showing the structure and bonding arrangement in diamond


Graphene
Graphene consists of a single layer of graphite which is a sheet of carbon atoms covalently
bonded forming a continuous hexagonal layer
It is essentially a 2D molecule since it is only one atom thick
It has very unusual properties make it useful in fabricating composite materials and
in electronics

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Graphene is a truly remarkable material that has some unexpected properties YOUR NOTES

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1.7.6 Predicting Shapes & Angles YOUR NOTES



Predicting Shapes & Angles
You will need to know and explain the shapes of the following molecules:
BeCl2
BCl3
CH4
NH3
NH4+
H2O
CO2
PCl5 (g)
SF6
C2H4
In order to write the correct shapes and structures of the molecules listed we need to
consider the number of valence electrons
BeCl2
Beryllium is in group 2, so has 2 valence electrons; Cl is in group 17, so has 7 valence
electrons
Both electrons are used to form covalent bonds with Cl and there are no lone pairs
Accommodating less than 8 electrons in the outer shell means than the central atom
is ‘electron deficient’
This gives a linear shape with bond angles of 180°

BCl3
Boron is in group 13, so has 3 valence electrons; Cl is in group 17, so has 7 valence electrons
All 3 electrons are used to form covalent bonds with Cl and there are no lone pairs
Accommodating less than 8 electrons in the outer shell means than the central atom
is ‘electron deficient’
This gives a trigonal planar shape with bond angles of 120°

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CH4 & NH3


Carbon is in group 14, so has 4 valence electrons; H is in group 1, so has 1 valence electron
All 4 electrons are used to form covalent bonds with H
This gives a tetrahedral arrangement with a bond angle of 109.5°
Nitrogen is in group 15, so has 5 valence electrons
Only 3 electrons are used to form covalent bonds with H and 2 are unbonded as a lone pair
This gives a trigonal pyramid arrangement with a bond angle of 107°

NH4+

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Nitrogen is in group 15, so has 5 valence electrons; H is in group 1, so has 1 valence electron YOUR NOTES
Only 3 electrons are used to form covalent bonds with H and 2 are used to form a dative 
covalent bond
This gives a tetrahedral arrangement
With a bond angle of 109.5° (similar to CH4)

The NH4+ ion


Other examples

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PCl5 (g)
Phosphorus is in group 15, so has 5 valence electrons; Cl is in group 17, so has 7 valence
electrons
All 5 electrons are used to form covalent bonds with Cl and there are no lone pairs
This gives a trigonal (or triangular) bipyramidal shape
With bond angles of 120° and 90°

Phosphorus pentachloride

molecule
C2H4
Each carbon atom is in group 14, so has 4 valence electrons, each hydrogen atom is in
group 1 so has 1 valence electron
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This gives a total of 12 electrons YOUR NOTES


There are 4 C-H bonds which use 8 electrons 
This leaves 4 electrons which are involved in the C=C
Therefore the overall shape is trigonal planar as there are three regions of electron density
for each carbon atom

Ethene molecule

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