13 Chemical Diffusion and Ficks Law

For the last 12 lectures we have been learning about mechanical systems and how to model me-
chanical systems that have linear constitutive laws relating mechanical variables, like position x
and velocity v, to forces. Today we are going to start in a new areachemical systemswhere
we will see that many of the lessons we learned from mechanical systems also apply in chemical
diffusion.

To understand the question we are going to try and answer, it is helpful to visualize a tank of
water that has fluid in it. The tank has length, depth, and width, but we are only going to consider
the fluid in one dimension along its length which we will call x. If there is a chemical in the
fluid, the concentration C of that chemical can change as a function of position in the tank; that is,
C can depend on x, so we will denote it by C(x). However, the concentration C(x) is assumed
not to vary with width or depth. We can plot C(x) over the tank, so that the value of the curve
represents the concentration of the chemical at the position x.
For today, we are going to assume that the chemical is at equilibrium, meaning that the con-
centration throughout the tank is allowed to vary as a function of x but is not allowed to vary with
time. Also, we are going to assume that the volume, V , of the tank stays constantbecause it
makes things easier.
Note that as a result of the equilibrium assumption, the amount of mass in any given volume V
is constant.16

16
R
(because mtotal = V
C(x)dxdydz, so if C(x) is not changing with time, mtotal is not changing with time either)

42
 Also note that if I draw in two positions x1 and x2 , I get that the volume between them is
V = Adx, where A is the cross-sectional area in the width-depth plane of the tank and dx is the
difference between x1 and x2 .
If there are no reactions taking place and there is no accumulation of the chemicalfor in-
stance, the chemical is not precipitatingthen conservation of mass implies that the amount of
mass going into the volume V must be equal to the mass leaving V . We call the rate at which mass
enters the volume the flux F , which generally varies with x. We define the flux to be positive at
a particular location x1 if there is mass of the chemical diffusing from left to right at x1 . Hence,
conservation of mass implies that the flux F (x1 ) of chemical into V at x1 must be the same as the
flux F (x2 ) of chemical out of V at x2 ; that is, F (x1 ) = F (x2 ).
Now we ask the question: What drives the fluxwhat makes it positive or negative? If
C(x) = constant, then the concentration is the same everywhere and we do not expect any flux
of chemical. To understand this, think about the milk that I poured into my coffee in lecture; if
the coffee is stirred and the milk is equally dispersed throughout the fluid, it would be very strange
to have the milk start diffusing so that it was at a higher concentration in one place than another.
Therefore, we dont expect F (x) to depend on the absolute amount of chemical present. Said in
terms we have used before in mechanical systems, we dont expect a constitutive law of the form
F (x) = DC(x)where D is some constantbecause that would imply that positive concentra-
tion leads to positive flux of the chemical to the right in the diagram.
Instead, if there is more chemical to the right, we expect the chemical to diffuse to the left.
Alternatively, if there is more chemical to the left, we expect the chemical to diffuse to the right.17
The next simplest choice we can make is to propose that at a given x (say, x1 or x2 in the figure),
the propensity of the chemical to flow in the positive x direction is a function of the derivative
dC(x)
dx
of C rather than C(x). And, thinking back to mechanical systems, the simplest choice we
could make is to make the constitutive law be linear with respect to the derivative of C. Lastly,
what should the sign of the constant be? Well, if the concentration being higher to the right implies
flux to the left, the constant must have a negative sign.
These observations put together are called Ficks law, which states that

dC(x)
F (x) = D A
dx
, where D > 0 is the constant of proportionality and A is again the cross sectional area (since flux
is occuring everywhere in that cross sectional area). It is worth noting that just like in mechanical
systems, this linear relationship only occurs because we have a highly controlled environment
the fluid is still, it is probably very uniform, and the chemical being introduced is also uniform.
If this were a natural system, with all the environmental factors that could be introduced, a linear
relationship between flux and the derivative of concentration with respect to position x probably
could not be expected.
What should you remember from today? The key thing is that diffusion is driven by flux, and
the simplest model of flux is called Ficks Law.

17
Keep in mind that despite the fact that there is flux, the concentration is assumed to be in equilibriumC(x) is
still constant with respect to time even though individual atoms of chemical are diffusing across the boundaries.

43