Recall…

The only bond which

is truly non-polar is
between the
____same___ atoms.

The nature of the bond can be affected by the size of the

particles of the particles, their charge and their
electronic configurations.
Recall…

Higher distortion higher covalent nature of the

bond, lower distortion higher ionic nature.
Recall…

Covalent, polar covalent and ionic bonding can be

considered as forming a spectrum. As the difference in
electronegativity increases, the bonds become more
polar then ionic.
Electronegativity and Bond Type

Electronegativity difference increases

The type of bond or degree of polarity can usually be

calculated by finding the difference in electronegativity
of the two atoms that form the bond.
We should always describe the bond as “
strongly polar” or “predominantly covalent
and ionic”…
Recall…

Electronegativity is the tendency of an atom in a

molecules to attract a pair of bonding electrons in a
covalent bond.
Polarity is caused by a difference in electronegativity
between two bonded atoms.
 Size mismatch…

The greater the degree of polarization, the

lower the melting point and the greater the
solubility in non-polar solvents.
• The ability of a cation to distort an anion is known as
its polarization power and the tendency of the anion to
become polarized by the cation is known as its polarizability
• Greater the polarization power or polarisability of an ion,
greater will be its tendency to form a covalent bond.
• Polarization affects the extent of electron sharing in all ionic
compounds.

Bond Polarity
The polarizing power and polarizability that enhances the
formation of covalent bonds is favoured by

• Small cation: the high polarizing power stems from the greater

concentration of positive charge on a small area. This explains why
LiBr is more covalent than KBr (Li+ 90 pm cf. K+ 152 pm).
• Large anion: the high polarizability stems from the larger size
where the outer electrons are more loosely held and can be more
easily distorted by the cation. This explains why for the common
halides, iodides, are the most covalent in nature (I- 206 pm).
• Large charges: as the charge on an ion increases, the electrostatic
attractions of the cation for the outer electrons of the anion
increases, resulting in the degree of covalent bond formation
increasing.
Large cations are to be found on the bottom left of
the periodic table and small anions on the top right.
Polarizing Power &
Polarizability
• Compounds having oxidation states +2 and +3 of these
elements have ionic bonds.
• Compounds having oxidation states above +3 generally show
covalent character.
• This is due to higher charge densities leading to greater
polarising power (cations distorting electrons of anion by
pulling it).

Bond Polarity
 Ionic Compounds With
Increasing Covalent Character
Aluminium Compounds

aluminium oxide:
ionic with covalent
character

aluminium chloride:
covalent with ionic
character
 Ionic Compounds With Covalent Character
1. AlF3 is ionic while AlCl3 and AlBr3 are predominatly
covalent.
2. Covalent character increases among period 2 chlorides
NaCl < MgCl2 < AICl3.
3. K2C03 is thermally more stable than Na2C03.
4. Melting point of LiF > LiCl > LiBr > LiI.
5. Li+ and Be2+ are small and have strong polarizing abilities.
Their compounds are more covalent than those of the
heavier elements in their groups.
 Covalent Ionic

Small cation (< ~100 pm) Large cation (> ~100 pm)

Large anion Small anion

High charges Low charges

Low ∆ electronegativity High ∆ electronegativity

Non metal – non metal Metal – Non metal

Fajan's rules for predicting whether a bond is predominantly

covalent or ionic.
• Increase in oxidation state leads to decrease in basic
character of the oxide and vice versa. For example, MnO is a
basic oxide whereas Mn2O7 is an acidic oxide. In the case of
permanganate ion, MnO4 – , bonds formed between
manganese and oxygen are covalent.
• Hence, compounds with higher oxidation states tend to be
good oxidizing agents e.g. KMnO4 and K2Cr2O7 as they tend
to accept electrons (itself reduced) and become stable lower
oxidation states.

Polarizing Power of 1st Row

d-block Elements
• d electrons are not as good at shielding the positive charge
of the nucleus.
• Transition metal atoms and ions therefore have greater
polarizing power than the atoms and ions from the s and p
block.
• The poorly shielded nucleus attracts lone pairs of electrons
strongly. Hence, dative covalent bonds are formed between
the central atom and the ligands (complex ion).

Polarizing Power of 1st Row

d-block Elements
 Ionic compound that
does not exist….

http://www.aluminumsulfate.net/Aluminum-Carbonate.html

Al3+ cation is so small and highly polarizing that completely

distorts the large CO32- ion into self-decomposition.
Instead of Al2(CO32-)3, carbon dioxide is formed, leaving
behind Al2O3.
• Not all atoms attract electrons with the same force.
• Atoms with high electronegativity (F>O>N) exert a greater
pull on electrons than atoms with lower electronegativity.
• In a bond, this leads to unequal sharing of electrons between
the atoms, as electrons will be drawn closer to the atom with
the higher electronegativity.
• The separation of charge is called a dipole moment and the
overall distortion of charge referred to as polarization.
• The larger the difference in electronegativity, the larger the
dipole moment.

Bond Polarity &

Dipole Moments
• In the CH3Cl molecule, chlorine is more electronegative than
carbon thus chlorine attracts the electrons in the C—Cl bond
toward itself.

One end of C-Cl is positive and the

other end is negative, this bond is
described as a polar bond. 
The vector will point from the partial
positive charge to the partial negative
charge and run parallel with the bond
between 2 atoms. 

Charge separation (polarity) in a

covalent molecule gives the molecule
some ionic character.
Bond Polarity &
Dipole Moments
• A polar molecule always contains polar bonds, but some
molecules with polar bonds are nonpolar.

CO2 is a linear molecule with 2  bond dipoles that are

equal and oppositely directed therefore the bond
polarities cancel and the molecule is nonpolar.
Bond Polarity &
Dipole Moments
• A molecule can be described as polar if it has a permanent
dipole or molecular dipole.

• O-H bonds in water as polar covalent bonds since oxygen is

significantly more electronegative than hydrogen. 
• The net dipole is in the "middle" of the molecule (in green). 

Bond Polarity &

Dipole Moments
• Hence, for a molecule to have a net dipole, the molecule
must have some polar bonds and the dipoles must not
cancel out as a result of the symmetry of the molecule.
• Cancellation of dipole moments depends on the shape
of the molecule (stereochemistry) as well as the
orientation of the polar bonds.

electronegativity is not the

only factor. Bond Polarity &
Dipole Moments
• Symmetry prevents polarity. Polar molecules MUST have an
asymmetrical structure to be polar.
• When electrons shifted to one side of the molecule, the
molecules become asymmetrical.
• Hence, any pull on electron in one direction is not cancelled
by a pull on electrons in the opposite direction.
Bond Polarity & Dipole Moments
Examples of Symmetrical Molecules With
Polar Bonds
• When molecules are symmetrical even though the bonds
are polar, the charge distributions effectively cancel each
other out; see below

24
Practice 1
• Which cations will have the greatest polarising power?
Consider the size (radius) of the ion and the charge on it.

• Which anions will be most easily polarised?

• Which ionic compound of group 1 and 7 would make a

compound with the least covalent character?
Practice 2
• What will the predominant bond type be in:
(a) BeCl2
(b) BF3
(c) AlCl3
(d) CO
(e) NaCl
Practice 3
Predict whether the following will be polar or non-polar
molecules:
(a) PH3
(b) CF4
(c) HCN
(d) BeCl2
(e) C2H4
(f) ClF
(g) F2
(h) BF3
27
Bond Length
As _______ electrons are shared, the _______ the bond
length will be.

strong bonds are short …… weak bonds are long

Bond Strength
Bond strength is closely linked to bond length. The
________ the bond, the more _______ the bonding atoms
are pulled together. Bond enthalpy or bond energy is the
energy required to break the bond.
Strengths of Bonds
Discussion
• Refer to Tables 10 and 11 in the data booklet to discuss
the following:
• Explain the pattern in the relative strengths of the
single, double and triple carbon to carbon bonds in
relation to their covalent bond lengths.

Single

Double

Triple
Discussion
• Refer to Tables 10 and 11 in the data booklet to discuss
the following:
• Look at the strengths of the hydrogen-halogen bonds.
Explain any pattern you see in relation to their
covalent bond lengths.