IONIC BOND

Common mono-atomic ions of some groups of the representative

elements:

Some Lewis Structure of ionic compounds are given below

Energy changes during formation of ionic bond:

Ionic bond formation from gaseous atoms involves three steps:

1) Formation of gaseous cation – It involves loss of electrons by the

gaseous atoms and is an endothermic process. Energy required for
this process is ionization energy.
2) Formation of gaseous anion – It involves the gain of electrons by the
gaseous atoms and is an exothermic process. The energy released in
this process is called electron gain enthalpy.

The above process will become endothermic if divalent and trivalent

anions are formed because second and successive electron gain
enthalpies are positive.

3) Combining of oppositely charged ions to form ionic compound – It

involves the formation of crystal lattice by combining oppositely charged
ions.It is an exothermic process and energy released is called Lattice
Enthalpy (∆LH0).
For the stable ionic bonding the net effect of above three processes should
be exothermic i.e. total energy released is > total energy required

Factors that favor the formation of ionic bond:

(a) Ionization Enthalpy (Energy): Lesser the value of ionization enthalpy,

greater the tendency of the atom to form cation. For example, alkali
metals form cations easily because of the low value of ionization
energies.

(b) Electron gain enthalpy: Greater the value of electron gain enthalpy,
more the tendency of the atom to form anion .For example ,halogens
have high electron gain enthalpies within the respective periods and
form ionic compounds easily .

(c) Lattice enthalpy: It is the energy released when the close packing of
the gaseous ions of the opposite charge forms one mole of ionic solid.
Magnitude of lattice energy gives an idea about the inter-ionic forces
and it also gives the measure of the stability of the ionic compound
which depends upon the following factors.

(d)
1) Size of the ions—Smaller the size of the ion s, lesser the inter
nuclear distance and greater the inter ionic interaction, hence,
larger the magnitude of lattice energy
2) Charge on the ions--- Larger the magnitude of the charge on
the ions greater will be the attractive forces and higher the
negative value of lattice energy.

Lattice Enthalpies of Halides of Alkali Metals (kJ mol-1)

In short the conditions are

1) Ionization enthalpy of the cation forming elements should be low.

2) Electron gain enthalpy of the element forming anion should be of

high negative value.

3) Lattice energy should also have high negative value.

Ionic Compounds:

The compounds that contain ionic or electrovalent bond are called

ionic compounds. And ionic bond is the force of attraction holding
the oppositely charged ions i.e. positive and negative charges.

Properties of ionic compounds:

1) Physical state

These exist in crystalline solids. Ionic crystals do not exist in the

form of molecules but exist in the form of ions. Ions are arranged in
a well defined geometry which constitutes ionic crystals. For
example in Sodium chloride crystal each sodium ion is surrounded
by six chloride ions and each chloride is surrounded by six sodium
ions as shown in the figure.
BLUE–CHLORIDE IONS RED- SODIUM IONS

2) High melting and boiling point

Because of strong electrostatic forces of attraction ionic compounds

have high melting and boiling point. The variation in melting point
depends on the charges on the ions and the ionic radii. Closer the
ions in the crystal, stronger will be the force of attraction and higher
will be the melting point. e.g. NaF to NaI. NaF (1270K), NaCl
(1073K), NaBr (1023K), and NaI (924K).

3) Solubility

Ionic compounds are soluble in water and other polar solvents .

This is due to the strong electrostatic interactions between the ions
and polar solvents.

4) Elecrtrical conductivity

Ionic compounds conduct electricity when in solution form or in

molten state. This is because ions are free to move in molten state
not in solid form.
 5) Ionic reactions

When dissolve in water ionic compounds split up into oppositely

charged ions.

6) Non-Directional

Since each ion is surrounded by oppositely charged ions uniformly

all around the ion so electric field is non–directional. Thus ionic
bond is called non–directional.

Lattice enthalpy of ionic crystals:

It is defined as the energy released when one mole of ionic crystal is formed
from it’s constituent ions in the gaseous state. It is represented as

The negative sign with lattice enthalpy shows that energy is released in the
process.

During the formation of ions the process is reversible and lattice enthalpy will
have +ve sign because energy is absorbed in the process. It is represented as
Lattice enthalpy can also be defined as the energy required to completely
separating one mole of solid ionic compound into gaseous ionic constituents.

The magnitude of lattice enthalpy depends upon:

Size of the ion: smaller the size of the ion, lesser is the internuclear distance,
higher will be the inter ionic attraction and larger will be the lattice enthalpy.

Charge on the ions: Larger the magnitude of charge on the ions, greater will
be the attractive forces between the ions and higher will be the lattice
enthalpy

Lattice enthalpies of some ionic solids:

BORN-HABER CYCLE FOR LATTICE ENTHALPIES

BORN and HABER devised a method to relate the lattice enthalpy of ionic
solids to other thermodynamic data. This is called BORN-HYBER cycle.

For example: During the formation of sodium chloride from metallic sodium
and chlorine gas, the energy changes during this process and BORN-HABER
cycle are as follows:
The overall process is considered to take place in the following steps:

Conversion of metallic sodium into gaseous sodium atoms:

The sodium atom can loose it’s electron in the gaseous state only. Thus, it
has to be sublimated. The energy required for sublimation i.e. converting one
mole of metallic sodium into gaseous sodium atom is called enthalpy of
sublimation (S)

Dissociation of chlorine molecule into chlorine atoms:

Energy required for converting gaseous chlorine molecule into chlorine atoms
is called enthalpy of dissociation (D)
Thus the enthalpy required for producing one mole of gaseous chlorine atoms
is D/2

Conversion of gaseous sodium atom into sodium ions:

The amount of energy required for converting one mole of gaseous sodium
atom into sodium ions in the gaseous state is called ionization enthalpy (I.E.)
Conversion of gaseous chlorine atoms into gaseous chlorine ions:

For converting one mole of gaseous chlorine atoms into chloride ions the
energy required is called electron gain enthalpy (∆ egH)

Combination of oppositely charged ions to form ionic solid crystal:

The oppositely charged Na+ and Cl- ions attract each other and form solid
NaCl with the release of energy. The amount of energy released when one
mole of solid crystalline compound is formed from gaseous ions of opposite
charges is called lattice enthalpy (U)
The overall energy change may be expressed as:

The enthalpy change for the above reaction is called enthalpy of formation
(∆ fH)

All the above steps can also be represented in the form of BORN-HABER
CYCLE as shown below.
According to Hess’s Law, the enthalpy of formation of one mole of NaCl
should be the same whether the reaction has taken place in one step or
through a number of steps.

Lattice enthalpy can be calculated by knowing the values of various

enthalpies. While calculating the value of Lattice enthalpy (+) sign should be
used for enthalpies absorbed and (-) sign for enthalpies released.

For example:- Lattice enthalpy for NaCl can be calculated as shown below.

1) Enthalpy of sublimation of sodium (S) = 108.5 kJmol-1

2) Enthalpy of dissociation of Cl2 (D)=243.0 kJmol-1

3) Ionization enthalpy of sodium (IE)= 495.2 kJmol-1

4) Electron gain enthalpy of chlorine (∆ egH) = - 348.3 kJmol-1

5)Enthalpy of formation of NaCl (∆ fH)= - 381.8 kJmol-1

Substituting the various values in the equation

Applications of BORN-HABER Cycle:

In addition to lattice enthalpies this cycle is also used for calculating other
properties.

1) Calculation of enthalpy of formation:

With the help of BORN-HABER cycle enthalpies of formation of unknown

compounds can be calculated. If the calculation for the enthalpy of
formation is coming out to be negative then the reaction is exothermic
and the compound formed will be stable. If enthalpy of formation comes
out to be positive then the reaction will be endothermic and the
compound formed highly unfavorable energetically. For example – NaCl2 is
not formed because enthalpy of formation calculated by BORN-HABER
cycle is highly positive although it has higher lattice enthalpy than NaCl.

2) Calculation of electron gain enthalpy:

The BORN-HABER cycle can also be used for calculating the electron
gain enthalpies of some elements which can’t be calculated easily
otherwise. By using the following equations electron gain enthalpy can be
calculated.