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Fick's laws of diffusion

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For the technique of measuring cardiac output, see Fick principle.

Fick's laws of diffusion describe diffusion and were derived by Adolf Fick in
1855. 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.
Contents [hide]
1 Fick's first law
2 Fick's second law
2.1 Example solution in one dimension: diffusion length
2.2 Generalizations
3 Applications
3.1 Biological perspective
3.2 Fick's flow in liquids
3.3 Semiconductor fabrication applications
4 Derivation of Fick's laws
4.1 Fick's 1st law
4.2 Fick's second law
5 History
6 See also
7 Notes
8 References
9 External links

Fick's first law

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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.

[edit]

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 is:

where

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is the "diffusion flux" [(amount of substance) per unit area per unit time], for example

measures the amount

of substance that will flow through a small area during a small time interval.
is the diffusion coefficient or diffusivity in dimensions of [length2 time1], for example

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Svenska

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(for ideal mixtures) is the concentration in dimensions of [amount of substance per unit volume], for example
is the position [length], for example
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 0.6x109 to 2x109 m2/s. For biological
molecules the diffusion coefficients normally range from 1011 to 1010 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

which for ideal mixtures is the concentration

gradient. 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 as:

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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), and is the chemical potential (J/mol).
If the primary variable is mass fraction ( , given, for example, in

where

is the fluid density (for example, in

Fick's second law

), then the equation changes to:

). Note that the density is outside the gradient operator.

[edit]

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

where
is the concentration in dimensions of [(amount of substance) length3], example

is a function that

depends on location and time

is time [s]
is the diffusion coefficient in dimensions of [length2 time1], example
is the position [length], example
In two or more dimensions we must use the Laplacian

, which generalises the second derivative, obtaining the

equation

Example solution in one dimension: diffusion length [edit]

A simple case of diffusion with time t in one dimension (taken as the x-axis) from a boundary located at position
where the concentration is maintained at a value
is

.
where erfc is the complementary error function. This is the case when corrosive gases diffuse through the oxidative layer
towards the metal surface (if we assume that concentration of gases in the environment is constant and the diffusion space (i.
e., corrosion product layer) is semi-infinite starting at 0 at the surface and spreading infinitely deep in the material). If, in its
turn, the diffusion space is infinite (lasting both through the layer with
and that with
), then the solution is amended only with coefficient in front of n0 (this might seem obvious, as the
diffusion now occurs in both directions). This case is valid when some solution with concentration n0 is put in contact with a
layer of pure solvent. (Bokstein, 2005) The length
is called the diffusion length and provides a measure of how far
the concentration has propagated in the x-direction by diffusion in time t (Bird, 1976).
As a quick approximation of the error function, the first 2 terms of the Taylor series can be used:

If

is time-dependent, the diffusion length becomes

. This idea is useful for estimating a diffusion length

over a heating and cooling cycle, where D varies with temperature.

Generalizations [edit]
1. In the inhomogeneous media, the diffusion coefficient varies in space,

. This dependence does not affect

Fick's first law but the second law changes:

2. In the anisotropic media, the diffusion coefficient depends on the direction. It is a symmetric tensor
law changes to

. Fick's first

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, it is the product of a tensor and a vector:

For the diffusion equation this formula gives

The symmetric matrix of diffusion coefficients

operator elliptic.

should be positive definite. It is needed to make the right hand side

3. For the inhomogeneous anisotropic media these two forms of the diffusion equation should be combined in

4. The approach based on the Einstein's mobility and Teorell formula gives the following generalization of Fick's equation for
the multicomponent diffusion of the perfect components:

where
are concentrations of the components and
various components and not to the space coordinates.

is the matrix of coefficients. Here, indexes i,j are related to the

The Chapman-Enskog formulas for diffusion in gases include exactly the same terms. It should be stressed that these
physical models of diffusion are different from the toy-models

which are valid for very small deviations

from the uniform equilibrium. Earlier, such terms were introduced in the MaxwellStefan diffusion equation.
For anisotropic multicomponent diffusion coefficients one needs a rank-four tensor, for example

, where i, j refer to the

components and , =1,2,3 correspond to the space coordinates.

Applications

[edit]

Equations based on Fick's law have been commonly used to model transport processes in foods, neurons, biopolymers,
pharmaceuticals, porous soils, population dynamics, nuclear materials, semiconductor doping process, etc. Theory of all
voltammetric methods is based on solutions of Fick's equation. A large amount of experimental research in polymer science
and food science has shown that a more general approach is required to describe transport of components in materials
undergoing glass transition. In the vicinity of glass transition the flow behavior becomes "non-Fickian". It can be shown that
the Fick's law can be obtained from the Maxwell-Stefan equations[1] of multi-component mass transfer. The Fick's law is
limiting case of the Maxwell-Stefan equations, when the mixture is extremely dilute and every chemical species is interacting
only with the bulk mixture and not with other species. To account for the presence of multiple species in a non-dilute mixture,
several variations of the Maxwell-Stefan equations are used. See also non-diagonal coupled transport processes (Onsager
relationship).

Biological perspective [edit]

The first law gives rise to the following formula:[2]

in which,
is the permeability, an experimentally determined membrane "conductance" for a given gas at a given temperature.
is the difference in concentration of the gas across the membrane for the direction of flow (from to ).
Fick's first law is also important in radiation transfer equations. However, in this context it becomes inaccurate when the
diffusion constant is low and the radiation becomes limited by the speed of light rather than by the resistance of the material
the radiation is flowing through. In this situation, one can use a flux limiter.
The exchange rate of a gas across a fluid membrane can be determined by using this law together with Graham's law.

Fick's flow in liquids [edit]

When two miscible liquids are brought into contact, and diffusion takes place, the macroscopic (or average) concentration
evolves following Fick's law. On a mesoscopic scale, that is, between the macroscopic scale described by Fick's law and
molecular scale, where molecular random walks take place, fluctuations cannot be neglected. Such situations can be
successfully modeled with Landau-Lifshitz fluctuating hydrodynamics. In this theoretical framework, diffusion is due to
fluctuations whose dimensions range from the molecular scale to the macroscopic scale. [3]
In particular, fluctuating hydrodynamic equations include a Fick's flow term, with a given diffusion coefficient, along with
hydrodynamics equations and stochastic terms describing fluctuations. When calculating the fluctuations with a perturbative
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approach, the zero order approximation is Fick's law. The first order gives the fluctuations, and it comes out that fluctuations
contribute to diffusion. This represents somehow a tautology, since the phenomena described by a lower order approximation
is the result of a higher approximation: this problem is solved only by renormalizing the fluctuating hydrodynamics equations.

Semiconductor fabrication applications [edit]

Integrated circuit Fabrication technologies, model processes like CVD, Thermal Oxidation, and Wet Oxidation, doping, etc.
use diffusion equations obtained from Fick's law.
In certain cases, the solutions are obtained for boundary conditions such as constant source concentration diffusion, limited
source concentration, or moving boundary diffusion (where junction depth keeps moving into the substrate).

Derivation of Fick's laws

[edit]

Fick's 1st law [edit]

in 1 dimension, the following derivation is based on a similar argument made in Berg 1977 (see references).
Consider a collection of particles performing a random walk in one dimension with length scale
be the number of particles at position at time .

and time scale

. Let

At a given time step, half of the particles would move left and half would move right. Since half of the particles at point
right and half of the particles at point
move left, the net movement to the right is:

move

The flux, J, is this net movement of particles across some area element of area a, normal to the random walk during a time
interval
. Hence we may write:

Multiplying the top and bottom of the righthand side by

and rewriting, we obtain:

We note that concentration is defined as particles per unit volume, and hence
In addition,

is the definition of the diffusion constant in one dimension,

In the limit where

.
. Thus our expression simplifies to:

is infinitesimal, the righthand side becomes a space derivative:

Fick's second law [edit]

Fick's second law can be derived from Fick's First law and the mass conservation in absence of any chemical reactions:

Assuming the diffusion coefficient D to be a constant, we can exchange the orders of the differentiation and multiply by the
constant:

and, thus, receive the form of the Fick's equations as was stated above.
For the case of diffusion in two or more dimensions Fick's Second Law becomes
,
which is analogous to the heat equation.
If the diffusion coefficient is not a constant, but depends upon the coordinate and/or concentration, Fick's Second Law yields

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An important example is the case where is at a steady state, i.e. the concentration does not change by time, so that the left
part of the above equation is identically zero. In one dimension with constant , the solution for the concentration will be a
linear change of concentrations along . In two or more dimensions we obtain

which is Laplace's equation, the solutions to which are called harmonic functions by mathematicians.

History

[edit]

In 1855, physiologist Adolf Fick first reported[4][5] 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. The 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.[6] 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 does happen),[7][8] we refer to such processes as non-Fickian, in that they are exceptions that
"prove" the importance of the general rules that Fick outlined in 1855.

See also

[edit]

Diffusion
Osmosis
Mass flux
MaxwellStefan diffusion
ChurchillBernstein equation
NernstPlanck equation
Gas exchange
False diffusion

Notes

[edit]

1. ^ Taylor, Ross; R Krishna (1993). "Multicomponent mass transfer". Wiley.

2. ^ Physiology at MCG 3/3ch9/s3ch9_2
3. ^ D. Brogioli and A. Vailati, Diffusive mass transfer by nonequilibrium fluctuations: Fick's law revisited, Phys. Rev. E 63,
012105/1-4 (2001) [1]
4. ^ A. Fick, Ann. der. Physik (1855), 94, 59, doi:10.1002/andp.18551700105 (in German).
5. ^ A. Fick, Phil. Mag. (1855), 10, 30. (in English)
6. ^ Jean Philibert, One and a Half Century of Diffusion: Fick, Einstein, before and beyond, Diffusion Fundamentals 2, 2005 1.1
1.10
7. ^ J. L. Vzquez (2006), The Porous Medium Equation. Mathematical Theory, Oxford Univ. Press.
8. ^ A.N. Gorban, H.P. Sargsyan and H.A. Wahab (2011), Quasichemical Models of Multicomponent Nonlinear Diffusion ,
Mathematical Modelling of Natural Phenomena , Volume 6 / Issue 05, 184262.

References

[edit]

W.F. Smith, Foundations of Materials Science and Engineering 3rd ed., McGraw-Hill (2004)
H.C. Berg, Random Walks in Biology, Princeton (1977)
R.B. Bird, W.E. Stewart, E.N. Lightfoot, Transport Phenomena, John Wiley & sons, (1976)
J. Crank, The Mathematics of Diffusion, Oxford University Press (1980)
Thermodynamics and Kinetics in Materials Science: A Short Course. Bokshtein, B. S. Mendelev, M. I. Srolovitz, D. J. Eds.
Oxford University Press: Oxford (2005) pp. 167171.
A. Fick, On liquid diffusion, Poggendorffs Annalen. 94, 59 (1855) - reprinted in Journal of Membrane Science, vol. 100
pp. 33-38 (1995)

External links

[edit]

Diffusion fundamentals
Diffusion in Polymer based Materials
Fick's equations, Boltzmann's transformation, etc. (with figures and animations)
Wilson, Bill. Fick's Second Law. Connexions. 21 Aug. 2007
[2]

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Categories: Diffusion Statistical mechanics Physical chemistry Mathematics in medicine

This page was last modified on 6 February 2015, at 20:20.

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