Fick's laws of diffusion

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From Wikipedia, the free encyclopedia
For the technique of measuring cardiac output, see Fick principle.

Molecular diffusion from a microscopic and macroscopic point of view. Initially, there are solute molecules on
the left side of a barrier (purple line) and none on the right. The barrier is removed, and the solute diffuses to fill
the whole container. Top: A single molecule moves around randomly. Middle: With more molecules, there is a
clear trend where the solute fills the container more and more uniformly. Bottom: With an enormous number of
solute molecules, randomness becomes undetectable: The solute appears to move smoothly and
systematically from high-concentration areas to low-concentration areas. This smooth flow is described by
Fick's laws.

Fick's laws of diffusion describe diffusion and were first posited by Adolf Fick in 1855

on the basis of largely experimental results.[1] They can be used to solve for the diffusion
coefficient, D. Fick's first law can be used to derive his second law which in turn is
identical to the diffusion equation.
A diffusion process that obeys Fick's laws is called normal or Fickian diffusion;
otherwise, it is called anomalous diffusion or non-Fickian diffusion.

History[edit]
In 1855, physiologist Adolf Fick first reported [1] his now well-known laws governing the
transport of mass through diffusive means. Fick's work was inspired by the earlier
experiments of Thomas Graham, which fell short of proposing the fundamental laws for
which Fick would become famous. Fick's law is analogous to the relationships
discovered at the same epoch by other eminent scientists: Darcy's law (hydraulic
flow), Ohm's law (charge transport), and Fourier's Law (heat transport).
Fick's experiments (modeled on Graham's) dealt with measuring the concentrations and
fluxes of salt, diffusing between two reservoirs through tubes of water. It is notable that
Fick's work primarily concerned diffusion in fluids, because at the time, diffusion in
solids was not considered generally possible.[2] Today, Fick's Laws form the core of our
understanding of diffusion in solids, liquids, and gases (in the absence of bulk fluid
motion in the latter two cases). When a diffusion process does not follow Fick's laws
(which happens in cases of diffusion through porous media and diffusion of swelling
penetrants, among others),[3][4] it is referred to as non-Fickian.

Fick's first law[edit]

Fick's first law relates the diffusive flux to the gradient of the concentration. 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 (see[5][6]) is in a molar basis:

where

 J is the diffusion flux, of which the dimension is the 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.
 φ (for ideal mixtures) is the concentration, of which the dimension is the amount
of substance per unit volume.
 x is position, the dimension of which is length.
D is proportional to the squared velocity of the diffusing particles, which depends on
the temperature, viscosity of the fluid and the size of the particles according to
the Stokes–Einstein relation. In dilute aqueous solutions the diffusion coefficients of
most ions are similar and have values that at room temperature are in the range
of (0.6–2)×10−9 m2/s. For biological molecules the diffusion coefficients normally
range from 10−10 to 10−11 m2/s.
In two or more dimensions we must use ∇, the del or gradient operator, which
generalises the first derivative, obtaining

where J denotes the diffusion flux vector.

The driving force for the one-dimensional diffusion is the quantity −∂φ/∂x, which
for ideal mixtures is the concentration gradient.
Variations of the first law[edit]
Another form for the first law is to write it with the primary variable as mass
fraction (yi, given for example in kg/kg), then the equation changes to:

where

 the index i denotes the ith species,

 Ji is the diffusion flux vector of the ith species (for example in mol/m2-s),
 Mi is the molar mass of the ith species, and
 ρ is the mixture density (for example in kg/m3).

Note that the   is outside the gradient operator. This is because:

where ρsi is the partial density of the ith species.

Beyond this, in chemical systems other than ideal solutions or mixtures,
the driving force for diffusion of each species is the gradient of chemical
potential of this species. Then Fick's first law (one-dimensional case) can
be written

where

 the index i denotes the ith species.

 c is the concentration (mol/m3).
 R is the universal gas constant (J/K/mol).
 T is the absolute temperature (K).
 μ is the chemical potential (J/mol).
The driving force of Fick's law can be expressed as a fugacity
difference:

Fugacity   has Pa units.   is a partial pressure of

component i in a vapor   or liquid   phase. At vapor

liquid equilibrium the evaporation flux is zero because  .

Derivation of Fick's first law for gases[edit]
Four versions of Fick's law for binary gas mixtures are given
below. These assume: thermal diffusion is negligible; the body
force per unit mass is the same on both species; and either
pressure is constant or both species have the same molar mass.
Under these conditions, Ref.[7] shows in detail how the diffusion
equation from the kinetic theory of gases reduces to this version
of Fick's law:

where Vi is the diffusion velocity of species i. In terms of species

flux this is

If, additionally,  , this reduces to the most common form of

Fick's law,

If (instead of or in addition to  ) both species have the

same molar mass, Fick's law becomes

where   is the mole fraction of species i.

Fick's second law[edit]

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:

where

 φ is the concentration in dimensions of [(amount of

substance) length ], example mol/m ; φ = φ(x,t) is a
−3 3

function that depends on location x and time t

 t is time, example s
 D is the diffusion coefficient in dimensions of
[length  time ], example m /s
2 −1 2

 x is the position [length], example m

In two or more dimensions we must use the Laplacian Δ = ∇2,
which generalises the second derivative, obtaining the
equation

Fick's second law has the same mathematical form as

the Heat equation and its fundamental solution is the same
as the Heat kernel, except switching thermal conductivity 

 with diffusion coefficient  :