N!

Number of ways on can distribute cation vacancies Wc (N  n )!n !


s s

Number of ways on can distribute anion vacancies N!

Wa 
(N  n )!n !
s s

The total number of ways of distributing these defects, W, is:

W  Wc Wa

The change in entropy due to introducing defects into a perfect crystal:

 N! 2
 N! 
DS  k lnW  k ln  2k ln(N  n )!n ! 

 (N  n )!n !
 s s   s s 

Concentration of defects, cont.

Simplify using Stirling’s approximation:

ln N! N ln N  N
thus:

DS  2k{N ln N  (N  ns ) ln(N  ns )  ns ln ns }
If the enthalpy change for the formation of a single defect is DHs
and then assume that the enthalpy change for the formation of n s
defects is nsDHs then the Gibbs free energy change is given by:

DG  ns DHs  2kT{N ln N  (N  ns ) ln(N  ns )  ns ln ns }

At equilibrium, Gibbs free energy of the system must be a  dDG 
minimum with respect to changes in the number of defects, n .  0
s dn s 
d
DH  2kT {N ln N  (N  n ) ln(N  n )
ln n }  0
n
s s s s s
dns
 d Concentration of defects, cont.
DH  2kT {N ln N  (N  n ) ln(N  n ) ln n }  0
n
s s s s s
dns
NlnN is a constant, so differential becomes zero
Differential of:
ln x is 1/x
xlnx is (1+ lnx)

DHs  2kT{ln(N  ns ) 1 ln ns 1}  0

(N  ns ) 
n  (N
   DHs 
DHs  2kT ln ns ) 
exp
s
2kT
 

 ns 
Since N >> Ns, approximate N-ns as N
  DHs
n    DHs 
s N exp  in molar
ns  N
 2kT  quantities
exp 
 2RT
 
where R is 8.314 J/mol K
DHs is the enthalpy required to form one mole of Schottky defects

Concentration of defects, cont.