Unit 4: Defect Chemistry and Defect Equilibria

Lecture 4.2
In this lecture, we will discuss about how impurity atoms induce the formation of defects. Also, an
important point is about their utility to remove certain defects which cannot otherwise be avoided
easily. We will also look at the calculation of equilibrium defects in an ionic solid which allows one to
calculate their concentration and understand the temperature dependence.

1) Concentration of Intrinsic Defects

Let us consider the formation of Frenkel defects in an halide, MX, i.e.

′
MM + XX ⇌ VM + Mi⦁ + XX

Changes in free energy (∆G) upon formation of ′𝑛′ Frenkel defect pairs at an
expense of ∆Gf energy per pair

G − Go = ∆G = n∆Gf − T ∆Sc (1)

where ∆Sc is the change in configurational entropy and is positive.

Equilibrium concentration of defects is found by minimizing ∆G w. r. t. n i.e.

the concentration at which free energy is minimum.

Change is entropy is given by

∆Sc = k lnW (2)

where W is number of ways in which defects can be arranged.

Now, as per the defect reaction shown above, number of Frenkel pairs (n)
would lead to the formation equal number of interstitials (ni) as well as
vacancies (nv) i.e.

n = ni = nv (3)

Assume, that total number of lattice sites = N

Number of ways to arrange the vacancies, Wv, is

N!
Wv = (N−n (4)
v )! nv !
Ways to arrange the interstitials (assuming that N lattice sites are equivalent to
N interstitial sites), Wi are
N!
Wi = (N−ni )! ni !
(5)

Total number of possible configurations,

𝑊 = Wv . Wi (6)

So, entropy change will now be

N! N!
∆Sc = k ln [((N−n)!n ) ((N−n)!n )] or
! !

N!
∆Sc = 2 k l n [(N−n)!n ] (7)
!

For large values of N, Sterling’s approximant lnN! = N ln N − N can be applied

which leads to

∆ Sc = 2k[N𝑙𝑛N − (N − n)𝑙𝑛(N − n) − n𝑙𝑛n] (8)

and total free energy change is

∆G = n∆ Gf − 2kT[N𝑙𝑛N − (N − n)𝑙𝑛(N − n) − n𝑙𝑛n] (9)

N N−n
= no Gf − 2kT [N 𝑙𝑛 ( ) + n 𝑙𝑛 [ ]]
N−n n
(10)

Figure 1 Equilibrium Vacancy Concentration

Now, if vacancies were stable defects, then at certain concentration, the free
energy change has to be minimum, as shown in the figure. Hence, at
equilibrium, we can safely write that
∆G
=0 (11)
∂n

We can also assume N − n ≃ N since number of vacancies is much smaller

than number of lattice sites in absolute terms.

This results in
n △Gf
= exp (− ) (12)
N 2kT

Now we know that, △ Gf = ∆ Hf − T∆Sv where ∆Hf = enthalpy of Frenkel

defect formation and ∆Sv = vibrational entropy change.

Hence, equation (12) further simplifies to

n ∆Hf ∆Sv
= exp (− ) . exp ( )
N 2kT 2kT
(13)
∆Sv
Assuming that exp ( )~1 as vibrational entropy change is very small, and
2kT
hence

n ∆Hf
= exp (− ) (14)
N 2kT
Similarly, for Schottky defects, you can work out that
n ∆Hs
= exp (− ) (15)
N 2kT
2) Intrinsic and Extrinsic Defects
Intrinsic behavior
 Defect which can be determined from the intrinsic defect equation and is
temperature dependent, increasing with increasing temperature.

Extrinsic behavior
 Extrinsic defects are defects caused by impurities consisting of aliovalent
cations.
 Defect concentration depends upon impurity concentration which is
constant and independent of temperature. Only at very high temperatures,
intrinsic behavior again dominates, and the cross-over temperature
depends upon the defect formation energy.

Example
Defect formation energies for some ceramic materials are

∆Hs (Mg O) ~ 7.7 eV, ∆Hs (NaCl) ~ 4 eV

Here, one can see relation with the melting point that melting point of MgO is
~2825C while it is ~801C for NaCl. So, at any given temperature NaCl will
have much larger defect concentration than MgO. However, at the same
homologous temperature, defect concentrations can be quite similar.

Interestingly, while highest achievable purity level in MgO is 1 ppm, in NaCl, it

is 50 ppm. Typically, these impurities consist of aliovalent cations which give
rise to defects, called as extrinsic defects. Thus the concentration of extrinsic
defects is much greater than intrinsic defect concentration in MgO. As a result,
defects in NaCl are likely to be intrinsic but MgO is most likely to contain
extrinsic defects.
3) Units for defect Concentration
n
Defect concentration fraction, , is nothing but the ratio of number of
N
defects, n, relative to number of occupied lattice sites N i.e. defect
concentration fraction. The denominator should actually be n+N but since,
N>>n, it can be approximated as n+N ~ N. Commonly used units for
concentration is #/cm3 or cm-3

Typical defect concentration in ceramics ~ 1 ppm

So if density of atoms in a solid ~1023 cm-3,

1 ppm concentration would be equivalent to 1017 cm-3

Conversion of mole fraction to number per unit volume can be following:

# 𝑔
𝐴𝑣𝑜𝑔𝑎𝑑𝑟𝑜′ 𝑠 𝑁𝑢𝑚𝑏𝑒𝑟 ( )∗ 𝑑𝑒𝑛𝑠𝑖𝑡𝑦( )
𝑚𝑜𝑙 𝑐𝑐
No. of formula units per unit volume = 𝑔
𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑊𝑒𝑖𝑔ℎ𝑡 ( )
𝑚𝑜𝑙
4) Defect Equilibria
Thermodynamics of Defect Reactions
A defect reaction can be treated like chemical reaction allowing us to relate the
thermodynamic variables like pO2, temperature to the free energy change or
enthalpy change which can be determined using experimental techniques. This
allow us to establish for example an equilibrium diagram between defect
concentration and pO2 helping us to identify various regions which may be
useful under practical conditions. For detailed chemical thermodynamics, you
should refer to the appropriate subject or books.

So, if a chemical system consists of 𝑛1 + 𝑛2 + − − +𝑛𝑖 moles of constituents

1, 2, 3, ………..,i, the partial molar free energy of Ith constituents given as
∂G
( ) = Gi = μi (16)
∂ni T,p,—n …..
i

Then according to the Gibbs Duhem equation, at equilibrium

μ1 dn1 + μ2 dn2 + − − +μi dni = O (17)

In a chemical reaction

aA+bB⇌cC+dD

Free energy change can be written as

acc .ad
∆G = ∆Go + RT 𝑙𝑛 ( D
) = ∆Go + RT 𝑙𝑛K
aaA .ab
B
(18)

where ∆G° → Free energy charge is standard state i. e. at unit activities.

At equilibrium, G = 0, hence

∆G° = −RT ln K (19)

acC .ad
D
where, K is equilibrium or reaction constant and K =
aaA .ab
B

In addition, free energy can be expressed as

∆G° = ∆H° − T ∆S ° = −RT ln K (20)

 ∆H° ∆S°
where K = K o exp (− ) where K o =
R R

which leads to K=Koexp(-Ho/RT) where Ko =So/R and R is the gas constant.

Alternatively,
d ln K ∆H°
=− (21)
d(1⁄T) R

This is an important outcome as it shows that we can treat the defects in a

solid as solutes in a solvent.

5) Summary

In this lecture, we learnt about estimating the defect concentration. The point defects are
thermodynamic defects and hence are stable. We looked at the thermodynamic considerations of
how one can calculate the equilibrium defect concentration in an ionic solid. It followed that defect
concentration is strongly dependent on temperature as it has an exponential dependence on it.
Hence, higher the temperature, one can expect very high defect concentration. Another aspect of
defects to be treated in a similar manner if one treats the solids consisting of small amounts of
impurities i.e. dilute solutions which is a realistic situation as defect concentration is not too large
considering the fractional concentration.