Summary of Chemistry Textbook: Section 2.

3 Covalent Bonding
- Chemical bond forms when outer-shell electrons come close enough together to interact
and rearrange themselves into a more stable arrangement one with a lower chemical
energy
- Chemical energy is the sum of the chemical potential energy of the particles and their kinetic
energy
- Electrostatic attraction between the positively charged nuclei and the negatively charged
electrons is the most significant source of the chemical potential energy
- As the two atoms approach one another, the positively charged nuclei repel one another, as
do the negatively charged electrons
- These repulsion forces increase the potential energy of the system
- At the same time, the oppositely charged particles are attracting one another causing
separating the atoms or ions will be such that the repulsive forces of the particles with the
same charge exactly balance the attractive forces between oppositely charged particles.
- It is in this stable arrangement that a chemical bond is formed
The nature of the covalent bond
- Simplest of all atoms is hydrogen
- Has just a single proton in its nucleus and a single electron occupying the space around it
- Hydrogen exists as diatomic molecules a pair of hydrogen atoms joined together H
2

- Molecule a discrete group of non-metal atoms covalently bonded to one another and
contain specific numbers of atoms in a set ratio
- E.g. a molecule of water contains two atoms of hydrogen bonded to one atom of oxygen;
the molecule is always the same whether the water is present in the solid, liquid or gaseous
phase
- Average radius of a hydrogen atom is 1.2 x 10
-10
m but distance separating the two nuclei in a
hydrogen molecule is just 7.4 x 10
-11
m
- This means that there must be significant overlap of the atomic radii of the individual atoms
when the molecule is formed
- Two atoms approach one another, electrostatic attractions and repulsions occur between
the positively charged nuclei and the negatively charged electrons
- The minimum overall energy of the system occurs at a separation of 1.74 A, where the
greatest amount of energy has been lost to the environment
- A hydrogen molecule has formed at this lowest point of the curve, most stable arrangement
of hydrogen molecule, each hydrogen atom has contributed its single electron to occupy the
space between the nuclei as a pair
- When a pair of electrons is shared between two atoms, a covalent bond forms
- Electrons of the bond make up a bonding pair
- Only one pair of electrons is occupying the space between the two nuclei, a single covalent
bond has been formed
- Valence-shell electrons that do not actually take part in the bond known as non-bonding
pairs (lone pairs)
- Non-bonding pairs are very important in determining the shape of the molecule which has a
significant effect on the properties of the substance
Lewis structures
- Can be constructed for covalently bonded molecules
- All valence electrons take part in bonding, non-bonding pairs also shown
- Useful in illustrating how each atom shares electrons to obtain an outer shell of eight
electrons
- Valence electrons represented by dots or crosses
- Covalent bond consists of a pair of bonding electrons between two atoms, a dot or cross
between the atoms represent a bond, while pairs of dots or crosses represent non-bonding
pairs of electrons
- Diatomic molecules consist of only two atoms covalently bonded to one another in order to
obtain a valence shell of eight electrons
- Diatomic molecules includethe elemental non-metals (e.g. O
2
, N
2
, Cl
2
, H
2
)
- Non-metal elements of group 0 already have eight electrons have very little tendency to
form bonds with other atoms
- Chlorine and bromine have seven electrons in valence shell and so will tend to share one
further electron in order to obtain a full outer shell
- Sharing one pair of electrons results in the formation of a single covalent bond between the
atoms
- Other six valence electrons do not take part in bond formation they form three pairs of
non-bonding electrons and will repel one another in space as far as possible
- Non-metals in group 6 only have six valence electrons therefore must gain a share of two
electrons this results in four electrons being shared between two atoms thus a double
covalent bond is formed
- Non-metals in group 5 only have five valence electrons therefore must gain a share of
three electrons this results in six electrons being shared between two atoms thus a triple
covalent bond is formed
The relationship between bond length and bond strength
- Triple covalent bond between nitrogen atoms is very strong and helps us to understand why
nitrogen is such an unreactive gas
- It requires a great deal of energy to break triple bond between the atoms and so allow
nitrogen to form new bonds with other atoms
- Amount of energy required to break a bond is known as the bond dissociation enthalpy
generally measured in kilojoules per mole of molecules dissociated
- Provides quantitative evidence that the bond strengths vary
- More electron pairs that are involved in a covalent bond the shorter the bond length and the
stronger the bond
- Bond length the distance between two nuclei at the point where a balance is achieved
between the attractive force pulling the nuclei together and the repulsive force of the two
positively charged nuclei pushing each other apart
- When there are two pairs of electrons shared between the two nuclei, the attractive force
pulling the two nuclei together will be greater and the balance between repulsion and
attraction will be at a shorter bond length
- Bond will be stronger due to the larger region of electron density between the two nuclei
- Triple bond attractive force pulling two nuclei together is greater therefore bond length
shorter
Shapes of molecules
- Most useful representation of molecules is the structural formula
- Each pair of electrons, bonding and non-bonding pairs is shown as a simple line
- Non-bonding pairs also shown as two dots
- Actual shape is shown
- Shape has an important part to play in determining the chemical and physical properties of a
molecule
- VSEPR theory electron pairs around an atom repel each other, the electrostatic repulsion
of pairs of electrons determines the geometry of the atoms in the molecule. Non-bonding
oairs and bonding pairs of electrons are arranged around the central atom so as to minimise
this electrostatic repulsion between the non-bonding and bonding pairs of electrons. The
relative magnitude of the electron pair repulsions is:
Non-bonding pair non-bonding pair > bonding pair non-bonding pair > bonding pair
bonding pair
- Shape depends on the number of bonding pairs and non-bonding pairs of electrons on
the central atom
- Bond angle is the angle between the atoms bonded to the central atom
- While non-bonding pairs of electrons can be important in determining the overall shape of a
molecule, not actually considered part of the shape
- Shape describes position of atoms only, however, non-bonding electrons repel other pairs of
electrons and so influence the final shape
- Negative charge centre or region refers to pairs of electrons on the central atom
- This includes non-bonding pairs and bonding pairs of electrons in single, double or triple
bonds
- Each double or triple bond is counted as one negative charge centre
- Diatomic molecules there are only two atoms to consider and so the molecule will invariably
be linear
- Polyatomic molecules are those that consist of more than two atoms covalently bonded to
one another
- This group encompasses great majority of molecules and includes significant ones such as
water, carbon dioxide and methane
- Consider unusual case of three pairs of electrons BF
3

- Three electron pairs will repel in such a manner as to form an equilateral triangle with a
bond angle of 120 degrees between each pair of bonds
- This arrangement of atoms is known as a trigonal planar shape
- Most common situation is the existence of four pairs of electrons, either bonding or non-
bonding, surrounding each atom
- Most widely spaced arrangement of four pairs of electron in 3D space is known as the
tetrahedral arrangement, in which each atom can be imagined to be at the vertex of a
regular triangular-based pyramid, bond angle 109.5 degrees
Electronegativity and bond polarity
- Electronegativity is a measure of the ability of an atom to attract the electrons in a bond
- Electronegativity increases from left to right and bottom to top of the periodic table
- Group 0 elements have undefined electronegativities, already have a full outer shell and so
they have little tendency to attract further electrons
- Comparisons between electronegativity values can be used to make generalisations about
the type of bonding and types of atoms forming a bond
- Elements such as fluorine, oxygen and nitrogen have high electronegativities whereas metals
have low electronegativities
- For atoms in a molecule to share the bonding electrons equally, the electronegativities must
be identical
- Description is true for the diatomic molecules of an element such as N
2
, O
2
, Cl
2
, H
2
and so on
- However, when the electronegativities are similar, the sharing of bonding electrons is
approximately equal
- The greater the difference in the electronegativities of the atoms in a compound, the more
uneven will be the sharing of electrons between them
- The extreme of unequal sharing is the formation of ions
- When ions are formed, one ion loses its valence electron completely and the other gains
valence electrons
- Difference in electronegativities is great the compound is likely ionic
- The closer the electronegativity values of the two atoms the more likely they are to form a
covalent compound by sharing electrons
- Bonds form between atoms with electronegativity differences of between 0.5 and 1.8 are
more likely to be polar covalent, while those with an electronegativity difference of zero will
form pure covalent bonds
EXAMPLE: Magnesium oxide
Magnesium electronegativity of 1.2
Oxygen electronegativity of 3.5
Therefore large difference of 2.3 suggesting that magnesium oxide is an ionic
compound
Supported by the location of magnesium in group 2, which is on the left-hand side of
the periodic table and therefore makes magnesium a metal
Oxygen is in group 6, which is on the right-hand side of the periodic table among the
non-metals
- If electrons are shared unevenly in a covalent bond, the bond is said to be a polar covalent
bond or a permanent dipole
- Such a bond can be identified using the symbol (delta)
- - and + used to indicate a slight negative and a slight positive charge respectively
- If a polar covalent bond occurs in a diatonic molecule, one part of the molecule will be more
negative than the other, due to having a larger share of the bonding electrons
- This is the case with diatonic molecules such as HCl and HBr
- The molecule is then described as a polar molecule
- When there is more than one polar covalent bond in a molecule, the shape of the molecule
must be considered
- It is possible to have molecules that contain polar bonds but overall are non-polar the
permanent dipoles cancel each other out
-
SECTION 2.3 EXERCISES
1. State the relationship between the group in the periodic table in which an element is
found and its number of valence electrons. The number of the group = number of valence
electrons
2. Of the substances in the following list, identify those that can accurately be described as
being composed of molecules. Carbon dioxide, ice, hydrogen chloride
3. State the total number of valence electrons and the number of non-bonding valence
electrons in each of the following molecules.
a) H
2
2, 2
b) Cl
2
14, 2
c) O
2
12, 4
d) HBr 8, 2
e) N
2
10, 6
4. Explain why the distance between atoms in these diatomic molecules increases as we
move down the group. The distance between atoms is called the bond length. The bond
length is the distance between two nuclei at the point where a balance is achieved between
the attractive force pulling the nuclei together and the repulsive force of the two positively
charged nuclei pushing each other apart. The bond lengths will increase as atomic radii
increases therefore due to radii increasing (F < Cl < Br < I) as you move down the periodic
table the bond lengths increase.
5. Determine which of the following pairs of atoms will have the greatest electronegativity
difference.
I Carbon and hydrogen difference: 0.45
II Hydrogen and oxygen difference: 1.34
III Sulfur and oxygen difference: 0.86
IV Carbon and chlorine difference: 0.61
6. Identify which atom in each of the following bond pairs will carry a slight negative charge
(-) and which a slight positive charge (+).
a) C H Carbon
b) B O Oxygen
c) P Cl Chlorine
d) S H Sulfur
7. Complete the table.
Molecule name Structural
formula
Are bonds polar?
Yes/No
Is the molecule
symmetrical?
Yes/No
Is the molecule
polar overall?
Yes/No
Oxygen (O
2
) No Yes No
Dibromomethane
(CH
2
Br
2)
Yes Yes
Carbon
disulphide (CS
2
)
Yes No Yes
Ammonia (NH
3
) Yes No Yes