Ionic Compounds

Introduction

 Ionic compounds are compounds which are formed due to the electrostatic forces
between ions. Hence, these are also known as electrovalent compounds.
 A complete transfer of electron takes place which is the reason for strong
electrostatic force.
 The electron donor is called cation and the electron acceptor is called anion.
 Formation of Ionic Bonds depends primarily upon:
1.Ease of formation
2.Electronegativity difference
3.Lattice enthalpy
Formation of Ionic Bond
Ease of formation
 Bonds are formed between atoms if this provides them with more stability.
More stability comes with the net loss of energy of the system.
 For cations to lose an electron, energy is needed to be supplied to them. This
energy is called ionization enthalpy.
 For anions to gain electrons, some energy needs to lost from them. This energy is
known as electron gain enthalpy.
 Since elements of Group 1 and 2 in the periodic table have the lowest ionization
enthalpies, and the elements in Groups 16 and 17 have the highest electron
gain enthalpies, formation of ionic bonds are favoured between metals of groups
1 and 2 and between non- metals of groups 16 and 17. This is because alkali
metals readily lose electrons and halogens readily accept electrons to complete
their octet.
Formation of Ionic Bond
Electronegativity difference
 Electronegativity is defined as the tendency of an atom participating in a
covalent bond to attract the bonding
electrons. Higher the electronegativity, the more that atom pull
the electrons from it’s bonding atom towards itself.
 But since in ionic bonds a complete transfer of electrons
occurs, the E.N. difference should be high so that the electron
is completely pulled by the anion from the cation.
 The electronegativity is fixed for each element according to
the Pauling Scale, invented by Linus Pauling in 1932. He
introduced the concept of electronegativity.
 Generally, in a periodic table, electronegativity increases from
left to right and from bottom to top.
 The minimum Electronegativity difference required for the
formation of an ionic bond is 1.7
 Electronegativity increases

Pauling’s Electronegativity Chart

Noble gases don’t have EN because they already have an octet

Formation of Ionic Bond
Lattice Energy & NaCl as an example

 The lattice energy of a crystalline solid is a measure of the energy released when

ions are combined to make a compound(exothermic).
 Lattice energy can also be defined as the energy required to break the ionic
bond(endothermic).
 Example: NaCl
Ionization Enthalpy for Na(g) Na+(g)+e- is 495.8 kJ/mol.
Electron Gain Enthalpy for the change Cl(g)+e- Cl-(g) is -348.7 kJ/mol only.
Ionization enthalpy is endothermic(+ve energy change).
Electron gain enthalpy is exothermic(-ve energy change).
Formation of Ionic Bond
Lattice Energy & NaCl as an example

 This implies, from the sum of the 2 enthalpies, that 147.1 kJ/mol of energy is
needed to be supplied in order to carry out this reaction.
But if Energy is gained, then stability must have reduced. Why then does this
reaction occur?
 The answer lies in the Lattice enthalpy, which is -788 kJ/mol for the reaction Na+
(g)+Cl-(g) NaCl(s). Thus, 147.1 kJ is more than compensated by the lattice
energy. Total= -788+147.1=-640.9kJ/mol
 The sum of LE, IE, and EGE gives the total heat/energy change that occurred. If
this amount is –ve(exothermic), only then would total energy of the system have
reduced and more stability achieved. If it is +ve(endothermic), then the reaction is
unlikely to take place on it’s own or even it does, then it is unstable.
General Properties of Ionic Compounds

 Hard and high melting and boiling points because of strong inter-molecular
forces.
 Dissolve in polar solvents like water. Solubility in non-polar solvents like
benzene, carbon tetrachloride is very negligible.

Let’s take an example of water and NaCl

to understand dissolution.

Water is a polar(covalent) solvent which

means that O has a partial negative charge
and H has a partial positive charge
(due to EN difference).
General Properties of Ionic Compounds -
Dissolution
Hence, when NaCl is dissolved in water, the Na+ atom is attracted by O atom, and Cl-
is attracted by H atoms, thus drastically weakening the forces between Na+ and Cl-
which ultimately break into free ions.

Because of the lack of polarity in non-polar solvents(as the name suggests), the
solvents aren’t able to attract the ionic solutes. Hence, the ionic compounds remain
attached and
don’t break into free ions.

Moreover, a surrounding procedure takes

place which further disconnects Cl- and Na+.
Weak
interaction
between Cl
and Na
General Properties of Ionic Compounds -
Dissolution
 Hydration reaction is a chemical reaction in which a substance combines with
water.
 Hydration energy (aka hydration enthalpy) is the amount of energy released
when one mole of ions undergo hydration.
 If hydration energy>lattice energy, then the solute is soluble because water is able
to provide the energy required to break the bond forces.
 If lattice energy>hydration energy, then the solute is insoluble because water is
unable to provide the energy required to break the bond forces.
General Properties of Ionic Compounds

 In aqueous solutions or in fused(molten) state, ionic compounds act as

conductors. This is because they break down into ions which are free to move
around in the solution.
 Since they are formed by non-directional bonds, they don’t exhibit isomerism.

Non-directional means that the

pull of the electrons does not
favour one atom over another.
In other words, we can’t say from
which anion the cation received
its electron.
General Properties of Ionic Compounds

Isomerism is the property in which the same compound with the same chemical
formula can have 2 or more plausible structures. Ionic compounds don’t show
isomerism because of non-directionality.
 Crystalline in nature. Crystalline means each small unit of the substance repeats
and has regular and ordered geometry. It can also be considered as the highest
degree of geometrical symmetry a substance can achieve.
 Brittle in nature. This is because in ionic compounds, the ions are rigidly held in a
lattice because the positive and negative ions are strongly attracted to each other
and difficult to separate. But if we apply a pressure on a layer of the compound
the layers shifts slightly. The like-charged ions in the lattice come closer.
Repulsive forces arise between like-charged ions throughout the surrounding
layers. Due to this high repulsive forces the lattice structure shatters easily.
Polarizing power

 Polarizing power refers to an atom’s ability to pull an electron toward

it, polarizing the atom the electron comes from. Since cations are positive, they
are able to attract electrons toward themselves. Anions are negative and so do not
attract more electrons.
 So, polarizing power can also be rephrased as the cation’s ability to attract the
electron cloud density towards itself.
 It follows that If the degree of polarization is quite small, an ionic bond is formed,
while if the degree of polarization is large, a covalent bond results. This is because
if the degree of polarization is high, then the cation would attract the electron
towards itself making a complete transfer of electrons difficult.
Polarizing power

 Tendency of anion to become polarized by the cation is known as it’s

polarizability.
 Polarizing power is directly proportional to charge density of the atom. If the size
of cation is small, then smaller volume, and hence higher charge density. The
nuclear will then strongly attract the electron, thus polarizing the anion, if the
cation is small in size.
This was an example of how polarizability works.
Fajan’s Rules
 Fajan’s rules show that even ionic compounds have partial covalent character. It
also helps to find which compound is more ionic.
 1: For a given cation, covalent character increases with increase in size of anion.
 This rule speaks about the polarizability of the anion. Larger the anion, less is the
effective nuclear charge that holds the valence electron of the ion in place. Since
the last electron is loosely bound in large anions, it can easily be polarised by a
cation, thereby making the compound more covalent.
Example: KF is more ionic than KI.
Fajan’s Rules

 2: For a given anion, covalent character increases with decrease in size of cation.
 This rule speaks about the polarising power of the cation. If the cation is smaller,
then we can say that the volume of the ion is less. If the volume is less, we can
conclude that the charge density of the ion would be high. Since the charge
density is high, the polarising power of the ion would be high. This makes the
compound to be more covalent.

Example: LiF is less ionic than compared to KF.

 We can also explain the above by using Electronegativity trend in periodic table.
Fajan’s Rules

 3: Covalent character increases with increasing charge either on cation or anion.

This is because to donate more electrons means more ionization enthalpy, which
leads to more unstability if complete transfer of electrons takes place. Hence
sharing would be preferred by the cation.

Example: SnCl4 is more covalent than SnCl2

 4: Covalent character is high for compounds with cations with pseudo noble gas
electronic configuration (n-1)s2p6d10 ns0 (usually transition metals) compared to
compounds with cations with noble gas electronic configuration ns2np6(common
with alkali or alkali earth metals). The explanation of this involves shielding,
other factors for size etc.
Other related info
 Unlike a molecule, which has a net charge of zero, a polyatomic ion behaves as a
single unit and has some net charge.
 Example: In Na2SO4 , (SO4-2) ion acts as a single unit or ion wherein Na donates
an electron to SO4-2 as a whole.
 We must take care while handling with certain compounds that may seem ionic at
first, but are actually covalent.
 Example: BeCl2, AlCl3 --- These might seem ionic at first because they’re made
of a metal and a non-metal, but are actually covalent because of their
electronegativity differences which are lower than the required 1.7. We can look
up the electronegativity chart here.
This is a good reason to remember the periodic table, which will help in taking a
good guess whether an element is ionic or not by remembering the general trend.
Finishing…
 There are many uses of Ionic compounds in our daily lives.
Their conductivity in aqueous state is often used to form electrolytes. Rock salt is
an inseparable part of our diet. Metal salts are commonly used in firework
displays. Baking soda, washing soda, bleaching powder etc. are all ionic
compounds. Many more such uses of ionic compounds exist. It is thus
crucial to study and understand them
in order to use them practically.
 Ionic compounds and related things can
be fully understood by studying and
comparing them with covalent
compounds.
What we have learnt:

 Formation of Ionic Bond depends upon-

1: Ease of formation
2: Electronegativity
3: Lattice Enthalpy
 General Properties of Ionic Compounds-
1: Hard and high melting and boiling points
2: Dissolve in polar solvents but don’t dissolve in non-polar solvents
3: Conductors in aqueous or fused state.
4: Crystalline structure
5: Brittle
6: Non-directional bonds, don’t show isomerism
What we have learnt:

 Polarizing power:
Ability of cation to attract/distort electron cloud density of anion
 Fajan’s Rules:
1: Polarizability of anion
2: Polarizing power of cation
3: Increasing charge leads to more covalent character
4: Transition metals tend to form more covalent compounds than alkali
(earth) metals
 Few uses of (studying) ionic compounds
Thank You!