September 26, 2001

Reading: Chapter V
Homework: 5.2, 5.4, 5.6, 5.8, 5.10, 5.11, 5.12
Example 1. Vacancy concentration in a crystalline solid material.
A vacancy in a crystal is created when an atom moves from inside bulk to the surface.
This requires input of energy (work) because surface atoms, binding to less number of
neighboring atoms, are higher in energy than bulk atoms. In other words, creation of
vacancies requires breaking of bonds. Now, consider a perfect crystal containing N
atoms. Suppose we create n vacancies by moving n atoms inside bulk to the surface.
Initial

N atoms
N sites

Final

N atoms
n vacancies
(N+n) sites

We examine the problem in terms of Gibbs free energy, assuming fixed temperature and
pressure.
Gi = U i TS i + PVi
G f = U f TS f + PV f
In solids, the PV term is usually very small at ordinary pressures, so we may neglect the
PV term. In such cases, there will be little difference between Gibbs free energy (G) and
Helmholtz free energy (A).
Now, U f = U i + nu v
Where uv is creation energy of vacancy, i.e., the chemical potential of vacancy. It is the
increase of energy when one atom is removed from bulk and placed on the surface, as
this requires breaking of bonds. Another way to view uv is that it is the chemical-potential
difference between the bulk atom and surface atom, i.e., the energy cost to remove a bulk
atom minus the energy gain to create a surface atom.

The final entropy is given by,

S f = S i + nS v + S c
Where Sv is the increase in thermal entropy due to the heat that must be supplied to create
a vacancy. Sc is the configurational entropy, related to distributing N atoms and n
vacancies on (N+n) sites, i.e., spatial distribution of vacancies.

( N + n)!
N !n!
= k B {( N + n) ln( N + n) N ln N n ln n}

S c = k B ln conf = k B ln
So,

G f = U i + nu v T [ S i + nS v + S c ]
= U i + nu v nTS v k B T ( N + n) ln( N + n) + k B Tn ln n k B TN ln N
For equilibrium, at constant T and P, G must be a minimum. Since n is the only variable,
we differentiate G with respect to n, and set it to zero.

dG f
dn
Or

= 0 = u v TS v k B T ln( N + n) + k B T ln n

k B T ln

(I)

n
= u v + TS v
N +n

S
u
n
n

= exp v exp v
N +n N
kB
k BT

(II)

Differentiating (I) again with respect to n,

d 2G f
dn

k BT
k T
Nk B T
k T
+ B =
B >0
N +n
n
( N + n) n
n

Thus, Gf is minimized.
The equilibrium vacancy concentration in an elemental crystal is
S
u
n
xv =
exp v exp v
N
kB
k BT
Note that uv >0 (it costs energy to create vacancy). Thus, as T increases, the concentration
of vacancy increases. Diffusion and diffusion dependent processes are usually mediated
through vacancies.

Example 2. Vapor pressure over an elemental solid

Let u denote the energy needed to break off an atom from the solid and place it in the
gas phase--which is called energy of sublimation. (one may also views u as the chemical
potential of surface atom of the solid minus of that of gas.)
For simplicity, we assume gas behaving ideally (no interaction). We examine the problem
in terms of Helmholtz free energy, assuming fixed temperature and volume.
Initially, all atoms are assumed to be in solid phase. Finally, n atoms are evaporated into
gas due to a flow of heat into the container to provide the sublimation energy.
The increase in internal energy is
3
U = nu + nk B T
2
Where the second term is the kinetic energy of the gas phase.
For the gas phase,
S
S
dS =
dT +
dV
T V
V T
Also,
dU = TdS PdV
Then,
S
U
P = 0 for an ideal gas.

= T
V T
V T
So,
P
S

=
V T T

P
S
dS =
dT + dV
T
T V
Since, PV=RT for ideal gas, dV =

RT
dP at fixed T
P2

Then,

C
P RT
R
S
dS =
dT 2 dP = V dT dP
T P
T
P
T V

Thus, the increase of entropy in gas phase is

S

S = dS = S 0' + CV ln T R ln P per mole.

S0

Where S0 is the integration constant.

Or per n particles,
3
nk B ln T nk B ln P .
2
Where S0=entropy/atom (integration constant).
S = nS 0 +

For the solid, we assume the entropy per atom as Ss, the net change in entropy is nSs
(decreasing).
Thus, the total change in Helmholtz free energy of the whole (solid+gas) system is
3
3
A = U TS = U 0 + nu + nk B T Tn ( S 0 S s ) nk B T ln T + nk B T ln P
2
2
For equilibrium,

A
=0
n

A
3
3
= 0 = u + k B T T ( S 0 S s ) k B T ln T + k B T ln P
n
2
2

ln P =

S Ss 3
3
u
ln T + 0

2
2 k BT
kB

S Ss
u
u
3
32
P = exp T 3 2 exp 0
exp
~ T exp

2
kB
k BT
k BT
The above equation gives the vapor pressure of solid. Similar equation also gives the
vapor pressure for liquid with different values of u.