Chapter 5

• Diffusion
Diffusion is the movement of a substance from an area of high concentration to an area of low
concentration. Diffusion happens in liquids and gases because their particles move randomly from place
to place. Diffusion is an important process for living things; it is how substances move in and out of cells.

– Vacancy diffusion
Vacancy diffusion is a diffusion process whereby the random thermally-activated movement of
atoms in a solid results in the net transport of atoms. For example, helium atoms inside a balloon can
diffuse through the wall of the balloon and escape, resulting in the balloon slowly deflating.

– Interstitial diffusion
Interstitial diffusion is generally faster than vacancy diffusion because bonding of interstitials to
the surrounding atoms is normally weaker and there are many more interstitial sites than vacancy sites to
jump to. Requires small impurity atoms (e.g. C, H, O) to fit into interstices in host.

– Fick’s First Law

Fick's first law relates the diffusive flux to the concentration under the assumption of steady state.
It postulates that the flux goes from regions of high concentration to regions of low concentration, with a
magnitude that is proportional to the concentration gradient (spatial derivative), or in simplistic terms the
concept that a solute will move from a region of high concentration to a region of low concentration
across a concentration gradient. In one (spatial) dimension, the law can be written in various forms, where
the most common form is in a molar basis:

𝑑𝐶
𝐽 = −𝐷
𝑑𝑥
Where:

 J is the diffusion flux, of which the dimension is amount of substance per unit area per
unit time. J measures the amount of substance that will flow through a unit area during a unit time
interval.
 D is the diffusion coefficient or diffusivity. Its dimension is area per unit time.
 C (for ideal mixtures) is the concentration, of which the dimension is amount of substance per unit
volume.
 x is position, the dimension of which is length.

– Second Law
Fick's second law predicts how diffusion causes the concentration to change with respect to time.
It is a partial differential equation which in one dimension reads:

𝜕𝐶 𝜕2𝐶
=𝐷 2
𝜕𝑡 𝜕𝑥
where
 C is the concentration in dimensions of [(amount of substance) length−3],
 t is time, example s
 D is the diffusion coefficient in dimensions of [length2 time−1], example m2/s
 x is the position [length], example m
 – Temp effect
Higher temperatures increase the energy and therefore the movement of the molecules, increasing
the rate of diffusion. Lower temperatures decrease the energy of the molecules, thus decreasing the rate
of diffusion.
𝑄𝑑
𝐷 = 𝐷𝑜 𝑒𝑥𝑝 (− )
𝑅𝑇
– Slab- non-steady state
Nonsteady state diffusion is a time dependent process in which the rate of diffusion is a function
of time.