Chapter 4

Equilibrium Concentration of Point Defects

Equilibrium Concentration of Vacancies
Vacancy Defect in Crystal
 Gibbs Free Energy

The energy associated with a chemical reaction that can be used to do

work
G = H - TS

G = Gibbs Free Energy

H = Enthalpy of System

T = Temperature

S = Entropy
• If vacancies are present in the crystal then crystal disorder will
increase (i.e. Entropy of system will increase)

G = H - TS
If S increases then G decreases. The change in Gibbs Free Energy
is given as;

∆𝑮𝑽 = ∆𝑯𝑽 - T∆𝑺𝑽

∆H is change in enthalpy, ∆𝑆𝑉 is change in entropy

 The change in entropy is associated with the vibration of atoms
around the defects and also to arrangement of defects in
crystal. This can be described by using Boltzmann equation for
entropy of a disordered system.

∆𝑺𝑽 = k lnW

W is the number of ways of distributing ‘n’ vacancies over N

atomic sites. According to the probability theory, the expression
for W can be written as;
W = N!/(N-𝑛𝑣 )! 𝑛!

∆𝑺𝑽 = k ln [N!/(N-𝑛𝑣 )! 𝑛! ]
According to Stirling Approximation

lnN! = N lnN- N

So,
∆𝑺𝑽 = k {NlnN-(N-nv)ln(N-nv)-nv ln nv)}

∆𝑯𝑽 is change in enthalpy due to vacancy formation and it is associated

with bond energy. If enthalpy to form one vacancy is ∆ℎ𝑉 then
∆𝑯𝑽 = n ∆ℎ𝑉

Putting the values of ∆𝑯𝑽 and ∆𝑺𝑽 in the following equation will give us
the change of Gibbs free energy due to vacancies formation

∆𝑮𝑽 = ∆𝑯𝑽 - T∆𝑺𝑽

 At Equilibrium

𝑑∆𝐺𝑉
=0
𝑑𝑛𝑣
(−∆𝒉𝑽 )
𝒏𝒗 = N exp (in terms of enthalpy)
𝒌𝑻

Vacancy defect can be treated as chemical equilibrium.

In the case of vacancies we can write;
0 ↔ 𝑽𝑴
Here ‘0’ represents a normal occupied site in a crystal and 𝑉𝑀 is a
metal vacancy. Chemically, the reaction can be treated as a migration
of atom in a crystal to form vacancy
According to law of mass action;

The equilibrium constant for vacancy generation (𝐾𝑉 ) is written as

(−∆𝐺𝑉 )
𝐾𝑉 = 𝑛𝑣 = N exp
𝑅𝑇
OR
𝑛𝑣 (−∆𝐺𝑉 )
𝐾𝑉 = = exp
𝑁 𝑅𝑇
(−∆𝐺𝑉 )
𝑛𝑣 = N exp
𝑅𝑇

For single defect formation;

(−∆𝑔𝑉 )
𝑛𝑣 = N exp
𝑘𝑇
The change in Gibbs energy can be expressed in terms of
change in enthalpy and change in entropy

(−∆𝐻𝑉 ) (−∆𝑆𝑉 )
𝑛𝑣 = N exp + 𝑛𝑣 = N exp
𝑅𝑇 𝑅𝑇

If we ignore the entropy term then

(−∆𝑯𝑽 )
𝒏𝒗 = N exp
𝑹𝑻
 For a single vacancy defect, one can write:

(−∆𝒈𝑽 )
𝒏𝒗 = N exp
𝒌𝑻

OR

(−∆𝒉𝑽 )
𝒏𝒗 = N exp
𝒌𝑻
Equilibrium Population of Self-Interstitials in a
Monotonic Crystal
 Consider a monotonic crystal containing self interstitials atoms.
The creation of a self-interstitial leaves vacancy so we can write:

𝟎 ↔ 𝑴 𝒊 + 𝑽𝑴

𝑀𝑖 = Metal Interstitial, 𝑉𝑀 = Metal Vacancy

According to law of Mass action;

𝒏𝒊 𝒏𝑽 (−∆𝑮𝒊 )
( )( ) = exp
𝑵𝒊 𝑵 𝑹𝑻

𝟐
(−∆𝑮𝒊 )
Since 𝒏𝒊 = 𝒏𝑽 𝒏𝒊 = 𝑵𝑵𝒊 exp
𝑹𝑻
Ni = No. of interstitial sties
N = No. of occupied sites

𝒏𝒊 (−∆𝑮𝒊 )
= exp
𝑵𝑵𝒊 𝟐𝑹𝑻

𝟐
(−∆𝑮𝒊 )
𝒏𝒊 = 𝑵𝑵𝒊 exp
𝑹𝑻
 If N =𝑁𝑖
(−∆𝑮𝒊 )
𝒏𝒊 = 𝑵exp
𝟐𝑹𝑻
The Gibbs energy −∆𝑮𝒊 can be splitted into enthalpy and
entropy change

(−∆𝑯𝒊 ) (−∆𝑺𝒊 )
𝒏𝒊 = N [exp + exp ]
𝑹𝑻 𝑹𝑻

If Entropy term is neglected then

(−∆𝑯𝒊 )
𝒏𝒊 = N exp
𝑹𝑻
For a single self-interstitial defect;

(−∆𝒈𝒊 )
𝒏𝒊 = 𝑵𝑵𝒊 exp
𝟐𝒌𝑻

(−∆𝒉𝒊 )
𝒏𝒊 = 𝑵𝑵𝒊 exp
𝟐𝒌𝑻
Equilibrium Population of Schottky Defects in a Crystal
A Schottky defect consists of cation and anion vacancy that ensure electro
neutrality in a crystal.

The Schottky defects are present as equilibrium species, so the defects

population can be treated as chemical equilibrium.

Null ↔ cation vacancy + anion vacancy

0 = 𝑉𝑀 + 𝑉𝑋

𝑉𝑀 is cation vacancy whereas 𝑉𝑋 is anion vacancy

According to law of mass action; Expression for Equilibrium Constant for

Schottky Defect Formation is

𝑛𝑐𝑣 𝑛𝑎𝑣 (−∆𝑮𝑺 )

𝐾𝑆 = ( )( ) = exp (
𝑁𝑐 𝑁𝑎 𝑹𝑻

Nc=Na=N
𝑛𝑐𝑣 is the number of cation vacancies whereas 𝑛𝑎𝑣 is the number of anion
vacancies. N is the number of cation sites which is equal to number of
anion sites.

If 𝑛𝑐𝑣 = 𝑛𝑎𝑣 the we can write

2 (−∆𝑮𝑺 )
𝑛𝑠 = 𝑁2exp (
𝑹𝑻
(−∆𝑮𝑺 )
𝑛𝑠 = 𝑁 exp (
𝟐𝑹𝑻

Here 𝑛𝑆 is the number of Schottky defects per unit volume distributed over
the N sites per unit volume. The fraction of Schottky defects present is
given as

𝑛𝑆 (−∆𝑮𝑺 )
= exp (
𝑁 𝟐𝑹𝑻
 (−∆𝐻𝑆 ) (−∆𝑆𝑆 )
𝑛𝑆 = N [exp + exp ]
2𝑅𝑇 2𝑅𝑇

The Gibbs free energy is often replaced by the enthalpy of the

Schottky defects as the entropy term is neglected. So we can write

(−∆𝐻𝑆 )
𝑛𝑆 = N [exp ]
2𝑅𝑇
For a Single Schottky defect, we can write

(−∆𝒈𝑺 )
𝒏𝑺 = N exp
𝟐𝒌𝑻

(−∆𝒉𝑺 )
𝒏𝑺 = N exp
𝟐𝒌𝑻
Equilibrium Population of Frenkel Defects in a
Crystal
A Frenkel defect consists of a vacancy-interstitial pair in a crystal.
For a crystal of composition MX, the appropriate chemical
equilibrium for Frenkel defects on a cation sub-lattice is given as

Null ↔ cation vacancy + cation interstitial

0 ↔ 𝑽𝑴 + 𝑴𝒊

Here 𝑽𝑴 represents Cation vacancy, 𝑴𝒊 is a cation interstitial. If

there is no interaction between defects then according to law of
mass action; The Equilibrium Constant for Frenkel defects
formation on cation sites 𝐾𝐶𝐹 is written as;

𝒏𝒄𝒗 𝒏𝒄𝒊 (−∆𝑮𝒄𝑭 )

𝑲𝑪𝑭 = ( )( ) = exp (
𝑵 𝑵𝒊 𝑹𝑻
𝑛𝑐𝑣 is the number of cation vacancies whereas 𝑛𝑐𝑖 is the number of
cation interstitials, N is the number of occupied cation sites as Ni is
the number of interstitial sites. ∆𝑮𝒄𝑭 is the molar Gibbs energy for the
formation of Frenkel defect. R is gas constant, T is the temperature.

If 𝑛𝑐𝑣 = 𝑛𝑐𝑖 = 𝑛𝑐𝐹 , then

(−∆𝑮𝒄𝑭 )
𝒏𝒄𝑭 = 𝑵𝑵𝒊 exp (
𝑹𝑻

𝒏𝒄𝑭 is the Frenkel pair concentration. The fraction of Frenkel pair is given as;

𝒏𝒄𝑭 (−∆𝑮𝒄𝑭 )
= exp (
𝑵𝑵𝒊 𝟐𝑹𝑻
.
If N=Ni then

(−∆𝑮𝒄𝑭 )
𝒏𝒄𝑭 = N exp (
𝟐𝑹𝑻

(−∆𝐻𝑐𝐹 ) (−∆𝑆𝑐𝐹 )
𝒏𝒄𝑭 = N [exp + exp ]
2𝑅𝑇 2𝑅𝑇

For Single Frenkel defect;

(−∆𝒈𝒄𝑭 )
𝒏𝒄𝑭 = N exp
𝟐𝒌𝑻

(−∆𝒉𝒄𝑭 )
𝒏𝒄𝑭 = N exp
𝟐𝒌𝑻