Diffusion. Mechanisms.

MSE 327
Kostya Kornev, Clemson University

Diffusion
 Continuum Physics
Continuum – is an opposite to the discrete medium such as an atomic
lattice. In a continuum the mass is spread over the volume. Therefore, it is
naturally to introduce material’s density, i.e. mass per unite volume
Approximation!
Continuum physics: the objects of continuum physics are those where
the length scale of interest is larger than the size of a constituent particle, R,
and the interparticle distances, L.
Exp: Radius R of a Hydrogen molecule ~10 – 10 m
Average distance L between gas molecules ~10 – 7m 0.01
mm
Air cube with the side size 0.01 mm contains ~ 27 billions of
molecules!

In CP, the fields are the functions of space and time. For example,
density, temperature, concentration, pressure, etc.
Hypothesis of continuity
How continuous matter
really looks at the atomic
scale? This noise-filtered
image of a freshly
cleaved Mica is obtained
with the atomic force
microscope. It is
approximately 225
Angstrom wide. This
granularity of matter is
ignored in continuum
physics. (Source: Mark J.
Waner, PhD dissertation,
Michigan State
University, 1998. See
Lautrup’s textbook)
Where we can use Continuum Physics
and where we cannot use it? Luna Moth or Saturniid moth
Chemoreception and diffusion
Strategies for chemoreception
• The ideal chemosensory organ
– Responds to range of different chemicals
– Sensitive to low concentrations
• Labeled-line coding
– Individual receptors respond to single
chemicals
– Organ has many different cells types
– Higher sensitivity, lower generality 40,000 sex-odor receptors which
• Across-neuron coding are tuned to specific odors to the
– Receptors respond broadly but with extent that they are able to detect
different profiles a pheromone at a concentration as
– Stimuli encoded by response across low as 100 molecules in a cubic
receptor population centimeter!
– Lower sensitivity, greater generality
Moth scent tracking • Animals are able to follow
concentration gradient
• i.e. they sample not only
the concentration of
chemicals, but the rate of
change of this cemicals!

C / L ( C - is the
change of concentration,
L is the distance

L>> animal size>> size of a

single molecule
It is a good idea to use
continuum physics for
description of gas diffusion
 Insect odor receptor organs
Honeybee Saturniid moth

Fly Butterfly

Scarab beetle Hawkmoth

Fiber size ~ 1- 100 m, i.e. much greater than a size of a single molecule, ~
1 nm. It is a good idea to use continuum physics for description of gas
diffusion
Insects detect odorant molecules, pheromones, when these molecules drift
through lipid-coated nanopores having diameter of D~ 6–65 nm. Hence
collisions with the pore wall are critical in this problem. Since the pore
diameter is comparable with the size of pheromones, continuum physics
has to be used with a precaution
NATURE NANOTECHNOLOGY | VOL
6 | APRIL 2011, p253-260
Diffusion. Basic assumptions
n = N/V Concentration n = number of particles
N per unit volume V.
If we know the concentration n, we can find the
distance between two neighbors from the following
arguments.
Imagine that our particles are sitting in the nodes of
a cubic lattice.
d
The cell volume: V =d3
Due to definition, the particle concentration :

d n = 1/d3 d = (1/n)1/3

We can apply this simple model for a general case when the particles are
distributed randomly. Hence, the interparticle distance is estimated as d ~ 1/n1/3.
If the volume of a reservoir in question is much greater than d, we can
introduce the concentration field n = n(r) = n(x,y,z) which describes the particle
concentration as a continuum field changing at the distances r much greater
than d, |r| >>d.
 Forces due to pressure variations in fluids
Pressure P = Force Some gas occupies volume V. We are interested in finding
per unit area the particle distribution if the gas is subjected to the force f
(gravity for example).
z Take an elementary volume dV=Adz, where A is the
P(z+dz/2)
area of an elementary base, dz is the length of an
elementary cylinder.
Force acting on the lower base is P(z-dz/2)A, while the
force acting on the upper base is -P(z+dz/2) A. The z-
component of the force is
(x,y,z) dz
dFz= [P(z-dz/2) -P(z+dz/2)] A
Using Taylor expansion theorem

P(z-dz/2) = P(z)-[dP/dz](dz/2)+…
P(z-dz/2) dFz - (dP/dz)dzA= - (dP/dz) dV
The same trick is applicable to the y- and x- components
of the force, , the force density vector naturally
appears due to a non-uniform pressure distribution

f = - P = - ( P/ x, P/ y, P/ z)
 Pg atmospheric
Hydrostatics
pressure
1. No volume forces:
z
f=- P=-( P/ x, P/ y, P/ z)=0, ,
P=const
g
2. Gravity (g =9.8 m/s2 , is gas density, force density f ,
[f]=N/m3)
f= - P + g=0 , , P/ x =0, P/ y=0, P/ z=- g

, pressure does not change along the planes z=const. In incompressible

liquids:
P = Pg- gz
Ideal gas: P = nkBT, n is concentration, kB is the Boltzmann constant, T is
absolute temperature. Hence, the force balance gives
f = -dP/dz - mng = - kBTdn/dz - mng =0

dn/n = -(mg/kBT)dz ln (n/n0) = - (mg/kBT)z n = n0 exp(-mgz/kBT)

 Molecular interpretation of diffusion
The force density is expressed through the partial pressure
z of suspended particles

f = - P, , fx = - P/ x, fy = - P/ y, fz = - P/ z
For the partial pressure we have the ideal gas
law:
P = nkBT, n is concentration, kB is the Boltzmann
constant, T is absolute temperature. Hence, the
force acting on each particle is
Vz n = zn/ t
F = (1/n) f = - (1/n) P = - (kBT/n) n
Each particle in the gas is moving with velocity V
V=B F, where B is the particle mobility coefficient
V= - (BkBT/n) n
The flux is the number of particles crossing the given plane per unit
time: J = V n = - (BkBT) n
 Molecular interpretation of diffusion
The flux is the number of particles crossing the
z
given plane per unit time -
J = V n = - (BkBT) n=-D n
Fick’s law, where D is the diffusion coefficient

Compare with 14.12 which is the Fick’s law for

chemicals
Vz n = zn/ t It follows that any gradient of concentration
results in diffusion , i.e. even in the force field like
gravitational force field, when the concentration is
not uniform, the equilibrium is dynamic, i.e.
diffusion flux is not zero the particles
continuously move to reach this dynamic
equilibrium state:
Diffusion. Basic assumptions
What does it mean “inhomogeneous distribution”?
If we know the concentration n, we can find the
distance between two neighbors from the following
arguments.
Imagine that our particles are sitting in the nodes of
a cubic lattice.
d
The cell volume: V =d3

Due to definition, the particle concentration is:

d n = 1/d3 [ one particle per cell]
Therefore, d = (1/n)1/3
We can apply this simple model for a general case when the particles are
distributed randomly. Hence the interparticle distance is estimated as d ~ 1/n1/3.
If the volume of a reservoir in question is much greater than d, we can
introduce the concentration field n = n(r) = n(x,y,z) which describes the particle
concentration as a continuum field changing at the distances r much greater
than d, |r| >>d.
 General balance equation
Change in the density of species i
J(x) due to flux is:

dx
In 3-D:
The amount of species i, that accumulates in a volume ΔV in a Cartesian system
during the time interval δt can be found as: Divergence of the flux
Conserved measures amount of particles
quantity n ( n/ t) coming in/out of the given
elementary volume. If
Non-conserved particles(atoms, molecules, etc)
Production rate: are produced/consumed due to
quantities
generation rate + chem reactions, etc, one needs a
vanishing rate source/sink term .
 Mass balance. 2D for clarity

Consider an elementary volume dx dy h, where h is the

layer thickness measured perpendicularly to the screen.
In this volume, the amount of species A coming/leaving
through all four sides should be equal to the change of
dy the mass of species A stored within that volume. If the
dx
flux is J, the total mass flux of the species A through the
given elementary volume is:
y
-[Jx(x+dx)dy+Jy(y+dy)dx-Jx(x)dy-Jy(y)dx]h=dN/dt,
x
dimensions: (m/sm3) m2 =1/s (m/sm3) m2=1/s
n = number of
particles / unit
volume, V – The transport The rate of change of the
velocity, rate total number of particles
J=Vn N in the given volume
dx dy h per unit time
Reminder: Taylor series and linear approximations

J
As known from
J(x0) calculus, in
vicinity of any
point x0, any
continuous
regular function
J(x) can be
approximated as
x0 x x

J(x0 + ) J(x0) + (dJ/dx)| x0

+ (½) 2 (d2 J/dx2)| … (2)
x0

Where the slope is equal to the derivative dJ/dx taken at the

point x0. This expansion can be continued to higher order terms
(cubic, etc) and is called the Taylor series.
 Diffusion equation

Mass balance: -[Jx(x+dx)dy+Jy(y+dy)dx-Jx(x)dy-Jy(y)dx]h=dN/dt

Expressing N through the particle density:
N = n dxdy h, therefore, dN/dt = ( n/ t) dxdy h
i.e. the total discharge.

-( Jx/ x+ Jy/ y)= ( n/ t), or, using Fick’s law,

D( 2n/ x2+ 2n/ y2)= ( n/ t) Diffusion equation!

For mass concentration we will have = Mn, where M is the particle
mass, hence the diffusion equation takes on the form (14.47b)
written for 2D case
 General balance equation
J(x) Change in the density of species i
due to flux is:

dx
Cartesian system of coordinates
(x,y,z). In 3-D:
The amount of species i, that accumulates in a volume ΔV during the time
interval δt can be found as: Divergence of the flux
Conserved measures the amount of particles
quantity n ( n/ t) coming in/out of the given
elementary volume. If
Non-conserved particles(atoms, molecules, etc)
Production rate: are produced/consumed due to
quantities
generation rate + chem reactions, etc, one needs a
vanishing rate source/sink term .
 Diffusion equation: parameters and
dimensionless complexes
( n/ t) = D n Units:
[n] = 1/L3 (for example, L=meter)
Linear equation, i.e. if M is its solution, [t] = T (for example, T = second)
µM (µ=const) is also its solution; [ ] =1/L
If M & N are solutions, µM+ N are [D] = L2 /T
also solutions!
Example: diffusion of drugs through the skin:
What is a functional dependence of n on parameters?
Normalization or introduction of
n(0,t)=N n(L,t)=0 a new metric: x= LX, where X is
dimensionless
( n/ t) = D 2n/ x2
Chain rule: 2n/ x2 = (1/L) 2 2n/ X2
x
n(x,t) = N f(tD/L2, x/L)
 Steady state diffusion.
Example: diffusion of drugs through the skin:
A patch full of drags is attached to the skin. Assuming that the
outmost layer of the skin of thickness L is almost impermable
to the blood, find the flux of drugs diffusing through the layer
and entering the developed networks of capillaries.
n(0,t)=N n(L,t)=0 Model: at the surface of the skin the drug
concentration is kept constant, n(0)=N; at
the bottom of this layer the concentration is
zero because the drug are flowing away
x with the blood stream. Assume that the
drugs are not absorbed by the layer.

( n/ t) = D 2n/ x2
n(x,t) = N f(tD/L2, x/L) D d2n/ dx2 = 0
 Steady state diffusion.

D d2n/ dx2 = 0
n Ndf/ dX = C
N Nf = CX+B = Cx/L+B
Using boundary conditions:
x
At X=0 Nf=N or B=N;
At X=1, Nf=0 or C+N =0, ,
C = -N
n(x,t) = N f(tD/L2, x/L)
n (x)= N(1-x/L), f =(1-x/L)

Flux: J = - D dn/dx = DN/L The smaller the D, the smaller the

flux, the thicker the L the smaller
the flux…
At infinity
Steady state diffusion.
n=N Example: Gas absorption by a particle of activated
carbon.
Surrounding material: At infinity the concentration is
n=0 N; At the particle surface the concentration is zero.
Find the flux and concentration profile. Remember
r=R that the surface area A= 4 R2
In spherical coordinates: (D/r2)(d/dr)(r2dn/dr)=0
Introduce dimensionless variable: X=r/R r = XR
(1/R2X2)(d/dRX)(R2X2dn/dRX) = 0 or (d/dX)(X2dn/dX) = 0
New function n(r) = N f(r/R)

After first integration: (X2df/dX) = C,

After second integration: f = - C /X +B
Using boundary conditions: At X=1 f=0 or B=C; At X= , f=1 or B =
1, C = 1 : f = - 1 /X +1, n =N(- R /r +1)
Flux: q = - D dn/dr = -D NR/r2 ; Total flux: Q = A q= 4 NDR