Ionic solids & ionic bonding

• Alkali and alkaline earth metal halides & oxides

are ionic compounds.
• Thus, common salt, NaCl is typical ionic solid.
• Oxides of some transition metals are also ionic.
• For example, Fe2O3, Co2O3,
 Properties:

• Crystalline solids; have definite structure.

• Hard and brittle solids.
• High melting point & high boiling point.
• NaCl : 8010C; NaBr : 7470C; LiF : 84 0C ;
MgO : 28520C

• Readily soluble in water & other polar

solvents.

• Non- conductors in Solid state but conduct in

molten state & in aqueous solution.
 Ionic Bonding
• Ionic bond is the electrostatic attraction between
cations & anions. It is the force of attraction
between the oppositely charged ions.
• Some atoms lose electrons to form cations;
some gain electrons to form anions.
• For example:
• Na Na+ + e- ; Cl + e- Cl- .

• The cations & anions thus formed are held by

electrostatic attraction.
• These ions have inert gas electron
configurations; so stable.
• Ionic solids contain cations (M+) & anions (X-).
Thus, solid sod. chloride consists of Na+ & Cl-
ions
M+ + X- ----------- (M+X-)s
Animation of ionic bond formation
Animation of ionic bond formation
 Formation of ions
• Favourable factors for cation formation :
• Low ionization energy.
• - Large atomic size & few valence electrons.
• Example: Alkali metals, [ ] ns1 configuration.

• Favourable factors for anion formation :

• - High Electron Affinity, Higher
• Electronegetivity & one or two vacancies in
valence shell.
• Example: Halogens. [ ] ns2 np5 configuration.
 Favouable factors for ionic bond formation

• Factor favorable for cation & anion formation also favour

ionic bond (ionic compound) formation
• 1. Cation formation: M M+ + e
• Low Ionization Energy - large atomic size,
few valence electrons.

• 2. Anion formation: X + e X-
• High electron affinity, high electronegetivity
& few vacancies in valence shell.
• Favourable conditions to form Ionic Bond:

• Formed between electro positive element (group 1,2,13)

and electro negative element (group 15,16,17)

• E.N >= 2

• Lower I.E of one atom and high E.A of second atom

• Higher lattice energy

• Larger cations, smaller anions

 Close packing of ions
• Anions (larger) form close packed layers;
• Cations (smaller) occupy the holes created by anion
packing. Relative sizes of cations & anions important.
 Close packed structures
• C.N. 6 Close packing.

• C.N.8:
 Calculation of Limiting Radius Ratios
• Simple geometric calculations allow working out limiting r. r.
• Thus for C.N.=6 (see diagram)
• AB= a = r- + r- = 2r- ; AC= d = 2r- + 2r+
• Using Pythagoras’ theorem,
• AC2 = AB2 + BC2 = 2 a2 .
• So AC = d = (2)1/2 a
• Also, AC = 2r- + 2r+ and a = 2r-
• Thus, 2r- + 2r+ = (2)1/2 . 2r-,
• Or r- + r+ = (2)1/2 . r- ; dividing by r-
• r- + r+ / r- = (2)1/2
• Rearranging,
• r+ / r- = (2)1/2 – 1 = 0.414.
• This is the lower limit of r+/ r- for close packing with C.N.6.
• The upper limit of r+/ r- for C.N.6 is the lower limit of C.N. 8.
• It is 0.732
• a
 Limiting Radius Ratios & structures

Radius ratio = r+ / r – where r+ & r – radii of cation & anion,

 
respectively. r+ / r – is <1, since r+ < r – .
 Calculation of Limiting Radius Ratios

Octahedral Coordination: CN=6

rc + R A

2RA

rc + RA
a 2 RA  2  rc  RA 

 rc  RA  
2
 2
2RA RA 2

rc
 2  1  0.414
RA
 Cubic Coordination: CN = 8

2 RA  a

2( RA  rc )  3a

a 2(rc + RA)  rc  RA   3
RA
rc
 3  1  0.732
RA
2RA
 Rock salt (NaCl(s) ) structure

• Cl- ~ 1.81 Å; Na+ ~ 0.98 Å; rc/RA = 0.54

• Na+ is big enough for CN = 6 (but not 8)
– also big enough for CN =4, but adopts highest CN
possible.
• Face centered cubic (fcc) structure)
• 8 corners and Center of each face of the cube have a
Cl- ion.
• Na+ ions in the octahedral holes.
• C.N. of each ion is 6.
Rock salt (NaCl(s) ) structure
 Rock salt (NaCl(s) ) structure

• Rock salt (NaCl(s) ) structure

NaCl(s) structure
 How to draw this structure
• Draw a perfect square:
• Draw an identical square behind this one and offset a bit

• Turn this into a perfect cube

• Subdivide this big cube into 8 small cubes
• Then put the ions in
 CsCl
• Body centered cubic close (BCC) packed structure.
• Cl- ions occupy the eight corners of the cube & Cs+ ion
placed at the body centre of the cube.
• C.N. Cs + = 8 & Cl - = 8.
CaF2 Fluorite
 Example: ZnS

• S2- ~ 1.84 Å; Zn2+ ~ 0.60 – 0.57 Å;

r+/ r- = 0.326 – 0.408
• Zn2+ is big enough for CN = 4
• S2- in close-packed array
• Zn2+ in tetrahedral sites
• Zn:S = 1:1  ½ tetrahedral sites filled
• Which close-packed arrangement?
– CCP: Zinc blende
– HCP: Wurtzite structure
Zinc Blende (ZnS)
Rutile (TiO2)
 Lattice Energy: U
• Lattice energy, U:
• Energy is released when ions of opposite charge are
packed into the crystal lattice.
• The amount of energy released when gaseous ions
separated by infinite distance are fixed into the lattice
points to form one mole of ionic solid. For example,
NaCl(s).
• Na(g)+ + Cl(g)- NaCl(s). U = -775 k J mol-1.
• Higher the magnitude of U, more stable the ionic solid is.

• U depends upon the ionic charges, ionic size and the

lattice structure.
• ‘U’ can be theoretically calculated from Born- Lande
Equation.
 Born- Lande Equation

• Born – Lande equation:

• where: N = Avogadro number,

• A = Madelung constant; a constant for a given type of crystal lattice;

For NaCl(s) :FCC type: A = 1.74756;

CsCl(s) :BCC type: A = 1.76267.
Rutile (TiO2) : A = 2.408
CaF2 Fluorite : A = 2.51939

It can be seen that:

• 1. ‘U’ is directly proportional to product of ionic charge
• Larger the ionic charge, higher the lattice energy, U.
• 2. ‘U’ is inversely proportional to inter-ionic distance, r .
• Smaller the ionic size, higher is U.
• 3. U depends upon the crystal structure i.e. A
 Obtaining Born – Lande Equation

• In the ionic solids, the ions are packed closely.

• The ions are held by electrostatic attraction between the
oppositely charged ions.
• This attraction decreases the energy (potential energy).
• Energy (P.E) due to attraction between a pair of ions is
given by:

• where: z+, z- are ionic charges, & r is inter ionic distance, r

=r+ + r–

• For more than two ( a pair) ions, Eattr depends upon number
of ions and also their arrangement (type of crystal lattice).
 Obtaining Born – Lande Equation……

• So, for one mole of ions ( N ), & for a given type of

crystal lattice,

• where ‘A’ is a constant namely Madelung constant for

the crystal type.

• For NaCl(s), FCC structure, A = 1.74756, ; CsCl(s), BCC

structure, A = 1.76267 etc
 Obtaining Born – Lande Equation…….
• Repulsion occurs between electrons of ions when the ions are at
close distances.

• The repulsion energy, Erep. is

• given by Born eqn :

• where: ‘B’ is a repulsion coefficient & ‘n is Born’ exponent

• ‘n’ depends on configuration of ion
• Thus, He = 5 ; Ne = 7 ; Ar = 9 ; Kr = 10
• Lattice energy, U is the total of attraction & repulsion
energy holding the crystal together.
• Hence, U = Eattr. + Erep.

• At equilibrium distance (ro), the attractive & repulsive

forces balance and U is at the minimum.
• At equilibrium,
• dU/dr = 0 and the equilibrium distance, r = r0 . So
 Obtaining Born – Lande Equation…..

• Or at equilibrium:

• Rearranging to get value of ‘B’:

• Substituting this value of ‘B’ in equation 4, we get:

 Obtaining Born – Lande Equation…..

• Rearranging 5:

• n >1, so U is always –ve; indicates liberation of energy &

stabilization of crystal lattice.
• This equation is Born – Lande equation.
• Knowing the values for inter ionic distance, ‘r’, ionic
charges and geometry (A), U can be calculated.
• ‘U’ is in k J mol -1.
• ‘U’ for NaCl(s) from Born –Lande eqn. is –778 k J mol -1.
• This is close to the experimental value (from Born –
Haber cycle) of – 775 k J mol -1.
 Obtaining Born – Lande Equation…..

• When SI system is used, the Born- Lande equation takes

the form:

• where: εo= permittivity of free space = 8.854 x10-12 Fm-1.

 Modified Equations: Born- Meyer and Kapustisnki Eqns.
• Born- Lande approach treats the ions as hard spheres, and
assumes 100% ionic character to the bonds. Born and Meyer
modified the approach to include additional interactions (primarily
dispersion forces and covalency).
• The result was an equation of the form:

• Kapustinski further modified this equation by noting that A/ro did

not change much from lattice to lattice. His equation for

estimating U is:
• Estimate the lattice energy for NaCl.
• Given: N = 6.022x1023 /mol, e =1.6022-19, A = 1.747558,

• € = 8.854x10-12 C2/m , r = 282x10-12 m, n = 9.1

• Solution
Using the values given above, U is estimated using Born – Lande
equation as under:

• U = - [6.022x1023 * 1.747558 * (1.6022-19)2 /4π * 8.854x10-12 C2/m *

282x10-12 m] x (1 - 1/ 9.1)

• = - 766376 J/mol
• = - 766 kJ/mol
 U for CaO

 Lime, CaO, is known to have the same structure as NaCl

and the edge length of the unit cell for CaO is 481 pm.
Thus, Ca-O distance is 241 pm. Evaluate the lattice
energy, U for CaO.

 Ans: N, A, e, € values are same as for NaCl. z+ = 2 & z - = 2 ;

 ‘n’ is the average for Ca2+ ( 7 ) & O2- ( 9 ) = 8
• N = 6.022x1023 /mol, e =1.6022-19, A = 1.747558,
• € = 8.854x10-12 C2/m , r = 481 + 241= 722 x 10-12 m,
 Lattice Energies of Alkali Metals Halides (kJ/mol)

• F- Cl- Br- I-
• Li+ 1036 853 807 757
• Na+ 923 787 747 704
• K+ 821 715 682 649
• Rb+ 785 689 660 630
• Cs+ 740 659 631 604

• Lattice Energies of some Metal oxides (kJ/mol)

• Na+ 2481
• Mg 2+ 3791
• Al 3+ 15,916
• Effect of ionic size
• As the ionic radius of both Mn+ and Xn- increases, the lattice energy
decreases. The attractive force between the ions decreases and
they become easier to separate.
• e.g. LiBr 804 kJ mol-1 BeCl2 2983 kJ mol-1

• NaBr 742 MgCl2 2489

• KBr 671 CaCl2 2197
• RbBr 656 SrCl2 2109
• CsBr 644 BaCl2 2049

• Effect of ionic charge

• NaCl 776 kJ mol-1 CaCl2 2197 kJ mol-1
 Determination of lattice energy, U.
• No experimental to determine U.
• However, it can be computed from thermochemical data
using Born -Haber cycle.
• B-H cycle is based on Hess’s law of constant heat
summation.
• Hess’s law:
• The total heat change for a given reaction is constant; it
does not depend upon the path followed.”
 B- H cycle

• B-H cycle for ionic compound formation:

• Example: NaCl(s) formation from Na(s) & Cl2(g).

• Path I : One step reaction

• Na(s) + 1/2 Cl2(g). NaCl(s). ΔHf = enthalpy of

formation.

The same reaction can be carried out in 5 steps.

 B – H cycle

• Path II : Stepwise reaction: Energy

• 1. Sublimation of Na(s). S
• 2. Ionization of Na(g) IE
• 3. Dissociation of Cl2 (g). D
• 4. Formation of Chloride ion, Cl- (g) . EA
• 5. Formation of NaCl(s) from the ions. U
• According to Hess’s law:
• Heat change in Path I = Total heat change in Path II
• ΔHf = S + I.E + 1/2D + E.A. + U
• Hence, U = ΔHf - S - I.E - 1/2D - E.A
B – H cycle for NaCl(s)
B- H cycle for MgF2 .
 U for MgF2 .

• Δ Hf = Δ Hs + Δ Hd + (IE1 + IE2) + 2 EA1+ U

•  
• U = Δ Hf - Δ Hs - Δ Hd - (IE1 + IE2) - 2 EA1    
•   
•   = -1096.5 - 146.4 - 158.8 - (737 + 1449) - 2(-328)  
•   = -2931.7 kJmol-1
U / ΔHf for NaCl
 Solubility of ionic compounds
• Solubility or dissolution of ionic compounds involves Two
steps.
• 1. Breaking of ionic lattice (breaking of crystal structure)
to form ion pairs.  NaCl (s) Na+ (g) + Cl- (g)
Solvents of high dielectric constant weaken the
electrostatic attraction between the ions and break the
lattice.
• 2. Solvation of ions so that they are stabilized and do not
tend to form crystal lattice again.
Na+ (g) + Cl- (g) + solvent Na+ (aq) + Cl- (aq)
• Polar solvents solvate the ions due to ion- dipole
interaction.
• Water is a good solvent for ionic solids
 Solubility of ionic compounds - energy changes……

• When an ionic solid dissolves two energy changes are involved:

• 1. The ionic lattice must be broken down and the ions separated.
• The energy required is the lattice energy, U.
•  NaCl (s) Na+ (g) + Cl- (g)
•   This is an endothermic process, U + ve

• 2. The separated ions interact with the solvent molecules. If the

solvent is polar, the charged ions are attracted to one end of the
polar solvent molecules. The energy released is called the
solvation energy. With water, this is hydration energy.

• This process is exothermic.

•  Na+ (g) + Cl- (g) + solvent (water) Na+ (aq) + Cl- (aq)
ΔHsolvation
• Applying Hess’s Law
• ΔHsolution = U + ΔH solvation (hydration)
 Solubility of ionic compounds……

• ΔHsolution = U + ΔH solvation (hydration)

• Born - Haber cycle for dissolution:

 Solubility of ionic compounds……

• The enthalpy of solution can be exothermic or endothermic

depending on the size of the lattice energy (U +ve) and the solvation
(hydration) energy (ΔH -ve).
• e.g. for NaCl
• U = +776 kJ mol-1
• ΔHhydration = -772 kJ mol-1
•  
• Therefore, ΔHsolution = + 4 kJ mol-1
• For dissolution to occur, ΔHsoln must be very small or –ve .
• Ideally. for dissolution ΔHsolv > U so that ΔHsoln is –ve.

• Enthalpy of solution:

• The enthalpy of solution is the energy change when one mole of

solute is dissolved in a solvent to form an infinitely dilute solution.
 Polarization of Ions

• Polarization is distortion of the electron cloud

around the ions.
• Anions are large & so readily undergo
polarization by cations.
• Ability to undergo polarization is polarizability.
• Ability to polarize (distort electron cloud) is
polarizing power.
• Cations due to small sizes have high polarizing
power.
• Anions due to their large size have high
polarizability.
 Factors influencing polarization of ions.
• Fajan’s rules:
• Factors influencing polarization of ions are
summarized by Fajan. These are Fajan’s rules.
• 1. Size effects:
• Smaller the cation, higher is its polarizing
power & larger the size of anion higher is its
polarizability.
Small cations & large anions favor covalency
Polarizing power: Li+ > Na+ > K+ > Rb+ > Cs+
Polarizability : I- > Br- > Cl- > F- .
 Polarization of Ions
Polarization induces covalency in ionic compounds
 Fajan’s rules:
• 3. Electron configuration of cation:
• Polarization and hence covalency is favored if
the cations do not have a noble gas
configuration
Cu+ & K+ ions have almost similar ionic size; yet
Cu+ is more polarizing.
Cu+ ion has pseudo inert gas configuration
[Ar]18 3d10 4s0 ; but K+ ion has inert gas
configuration, [Ar]18 .
• 2. Charge effects:
• Higher the charge on the cation, higher is its
polarizing power; higher the charge on the
anion, higher is its polarizabilty.
• Large charge on either cation or anion favor
covalency.
Polarizing power: Li+ < Mg2+ < Al3+ < Ti4+ .
Polarizability: O2- > F-; S2- > Cl- .
 Effects of polarization on properties.

• In ionic compounds the cations are generally

small & anions are large; so anions are
polarized.
• Polarization of ions induces covalency in ionic
bonds.
• Lattice energy decreases due to polarization of
ions.
• Polarized ions are not spherical and so close
packing is not possible. This decreases the
lattice energy.
 Effects of polarization on properties…….

• This is reflected in properties.

• Example:
• Decrease in melting point.
- CaCl2: 782oC; HgCl2: 276oC
• Solubility ion organic solvents.
- LiCl soluble in alcohol
- AlCl3 & FeCl3 soluble in ether.
- AgCl is only sparingly soluble in water.
 Crystal Defects
• Stoichiometric Defects: Schottky defects
• NaCl lattice- normal NaCl lattice- Defect
• Normal lattice Defect lattice -Na+ & Cl- missing
• No lattice Vacancies Vacancies
 Crystal Defects
• Frankel defects:
• Cations missing from lattice points & occupying
interstices.
• Schottky defect

• 1. It decreases the density of the crystal.

• 2. It occurs in compounds with high Co-ordination

number.

• 3. It occurs in compounds in which cations and anions

are of similar size.

• Examples: NaCl, KCl, KBr, CsCl.

• Frankel defect:

• It does not decrease the density of the crystal.

• It occurs in compounds with low coordination

number

• It occurs in compounds in which cations and

anions differ in their size to a large extent.

Examples: ZnS, AgCl, AgBr, Agl

 Band Theory of metals
• It is extension of MOT to metal bonding.
• Metal is a giant crystal; large number of atoms combine.
• Large number of AOs combine to form large no. of MOs.
• Their energies are very close & appear as bands.
• Example: For Na: [ ] 3s13p0.
• The 3s AOs form 3s band; it is Valence band, V.B.
• 3p AOs form 3p band; it is empty, C.B; it is nearer to
V.B.
 Semiconductors & Nonmetals (insulators)

• Insulators Semiconductors
 Conduction by Semiconductors
• Small energy gap (band gap), ΔE between VB & CB.
Thermal excitation makes electrons flow from V.B to
C.B. This causes conduction.
 n-type semiconductor
• Doping Si with P or other element from 5th group, gives a
n-type semiconductor.
• P has an extra electron. Since the V.B. of Si is full , this
electron must go to higher energy C.B.
• These electrons now occupy a partially-filled C.B. and
can move easily between the orbitals of this band. Thus
enhance conductivity.
• Since extra electrons than in pure Si, this is n-type
semiconductor (n is for negative).
 p-type semiconductor

• Addition of a small amount of Al (or other element from

III group) to Si, replaces a few Si atoms from the lattice.
The impurity is known as ‘dopant’
• Al is 1e- short of Si. This creates a vacancy ( + hole) in
the V.B. of Si.
• Electrons in the V.B. can move from one orbital to
another within this band with only a small input of
energy. Thus enhance conductivity.
• The electrons from filled orbital move to fill this + holes
(vacancies) and as a result create new + holes.
This amounts to conduction by + holes and the
semiconductors are p-type.
Impurity Semiconductors : Doped semiconductors

In a silicon lattice, all silicon atoms bond perfectly

to four neighbors, leaving no free electrons to
conduct electric current. This makes a silicon
crystal an insulator rather than a conductor.
 p-type semiconductor

• A schematic diagram showing

• the solid crystal-lattice structure and bands
for silicon doped with Al,
• a p-type semiconductor.
• A vacancy ( hole) created in V.B.
• Electrons in the V.B. can move from one
orbital to another within this band with only
a small input of energy. Thus enhance
conductivity.
 n-type semiconductor.
• A schematic diagram showing
the solid crystal-lattice structure and
bands for silicon doped with
phosphorus( P), an n-type
semiconductor.

• Dopant (P) has 1e more.

Since the V.B. is already filled, the extra
electrons must go into the higher-energy
C.B.
• These electrons now occupy a partially-
filled C.B. and can move easily between
the orbitals of this band. Thus enhance
conductivity.
 Diodes

• A combination of two types of semiconductors (p-n ) is

known as a p-n junction, or a diode.
LEDs: Light Emitting Diodes