Activation energy for diffusion

We have now seen that atoms jump to the next neighboring position because of
thermal vibration.

In interstitial diffusion there is a chance that the neighboring sites are vacant.

However, in substitutional diffusion, it is bit complicated, since vacancy should

be present in the next neighbor position and then only there will be a possibility
of jump.

First we shall discuss the activation energy required for interstitial self
diffusion.

Atom from ground state, Gg

jumps to another ground state but
go through an activated state, Ga,
where it has to move its
neighboring atoms elastically.

As shown in the previous slide, atom cannot just exchange the place very
smoothly.

It has to move the neighbouring elements to clear the passage, since the size of
the atom is bigger than the void through which it will diffuse.

So the energy is required to move the neighboring atoms elastically.

Atoms vibrate with average energy and certain number of vibrations can have
enough energy to cross the barrier.

Average fraction or probability that atom will cross the barrier is exp(− ∆Ga RT )

 ∆G
∆G a 

Jump frequency can be expressed as Γi = ν exp − 
 RT 

2

Diffusion coefficient is expressed as D = Γi (∆x )

 ∆ Ga   ∆Gm   Q   Q 
D = ν ∆x 2 exp − 2
 = ν ∆x exp −
2
 = ν ∆x exp −  = Do exp − 
 RT   RT   RT   RT 

Now Q = ∆Gm = ∆H m − T∆S m activation energy for migration

 ∆H m  where D = ν ∆x 2 exp − ∆S m  pre exponential factor

D = D0 exp −  0
 RT   R 
∆H m activation enthalpy for migration

Activation energy can be determined from the diffusion coefficients
calculated at different temperatures.

 Q 
D = Do exp − 
 RT 
Q
ln D = ln Do −
RT

So if we plot lnD vs. 1/T, we can determine the activation energy for
diffusion, Q.
 Activation energy for substitutional diffusion

Here the main difference between the substitutional and interstitial

diffusion is that atom can exchange position only if vacancy is available next
to it with its own probability.

Average fraction of atoms, which will cross the barrier is

X V exp(− ∆Gm RT )

Jump frequency can be expressed as Γi = νX V exp −

∆Gm 

 RT 

Diffusion coefficient to a particular direction is expressed as D = Γi (∆x )2

 ∆Gm 
D = ν X V ∆x 2 exp − 
 RT 

 ∆G 

Equilibrium concentration of vacancies X V = exp − V 
 RT 

 ∆Gm + ∆GV   ∆Ga   ∆Ga 

D = ν ∆x 2 exp −  = ν ∆x exp −  = Do exp − 
2

 RT   RT   RT 

So Ga is the activation energy for self diffusion. It has two components;

activation energy for migration and activation energy for vacancy formation.

 ∆S   ∆H a   ∆H a 
D = ν∆x 2 exp a  exp  = Do exp − 
 R   RT   RT 

The same way again, as explained previously about the interstitial diffusion, we
can determine the activation energy.
 Activation barrier in FCC crystal

To understand the actual activation barrier, we need to consider the atomic
arrangement in three dimension.

Let us consider atomic arrangement of (111) plane of a FCC unit cell.

Suppose atoms 1-5 and vacancy at lattice point 6 are on the same plane. If atom
7 is located on the plane below this then atom 8 is located on the plane above it.

So if atom 2 jumps to 6, then it will have barrier plane with atoms 1, 7, 4 and 8.

barrier plane
 Activation barrier in a BCC unit cell

If the (100) plane is seen, the activation barrier is not clear.

Looking at one unit cell, it feels like it has one barrier plane.

However, actually it has two barrier planes and that is why it shows two humps
in the activation barrier plot
 Diffusion under chemical potential gradient

In self diffusion, suppose in a cubic crystal, when there is no concentration

gradient, the activation barrier for jump of atoms from plane 1 to 2 or plane 2 to 1
is the same and we can write
 ∆Ga 
Γ1→2 = Γ2→1 = ν exp − 
 RT 

Now suppose, we consider a system with chemical potential gradient between
plane 1 and 2 by
dµ ∆µ Interplanar distance is ∆x
=
dx ∆x
 [∆Ga − ∆µ / 2]   [∆Ga + ∆µ / 2] 

Then we can write Γ1→2 = ν exp −  Γ2→1 = ν exp − 
 RT   RT 

So we can write that diffusion rate under chemical potential gradient will be
higher than self diffusion, since Γ1→2 > Γ2→1