Diffusion and Fick's Laws

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Ficks-laws diffusion-coefficient random-walk concentration-gradient Stokes-Einstein

Core Idea

Fick's first law states that the diffusion flux J = −D(∂c/∂x) is proportional to the concentration gradient, with diffusion coefficient D. Fick's second law ∂c/∂t = D(∂²c/∂x²) describes how concentration profiles evolve in time, with Gaussian spreading: ⟨x²⟩ = 2Dt for one-dimensional diffusion. The diffusion coefficient for a gas scales as D ∝ T^(3/2)/p from kinetic theory; for a sphere in a liquid, the Stokes-Einstein equation gives D = kT/(6πηr), connecting diffusion to viscosity η and solute radius r. Self-diffusion, mutual diffusion, and tracer diffusion coefficients are distinct but related through the Onsager reciprocal relations.

How It's Best Learned

Solve the diffusion equation analytically for a point source and verify ⟨x²⟩ = 2Dt. Use the Stokes-Einstein equation to estimate the size of proteins from measured diffusion coefficients (a technique used in DLS).

Common Misconceptions

Explainer

Imagine dropping a crystal of food dye into still water and watching it spread. The dye does not move in any preferred direction — every molecule executes a random walk, jostling in all directions due to thermal motion. Yet the net result is clear: dye moves from regions of high concentration toward regions of low concentration. Fick's laws describe this macroscopic consequence of microscopic randomness.

Fick's first law captures the steady-state picture: the diffusion flux J (moles crossing unit area per unit time) is proportional to the local concentration gradient, with the diffusion coefficient D as the proportionality constant: J = −D(∂c/∂x). The negative sign is essential — flux flows in the direction of decreasing concentration. If the gradient is steep, flux is large; if concentration is uniform, flux is zero regardless of how high the concentration is. This law applies when the concentration profile has settled into a time-independent shape (steady state), as in a membrane separating two well-mixed reservoirs.

Fick's second law extends the analysis to transient situations, where concentration profiles evolve over time: ∂c/∂t = D(∂²c/∂x²). This is a partial differential equation whose solutions describe how an initial concentration distribution spreads and flattens over time. For a point source of material released at x = 0 and t = 0, the solution is a Gaussian profile whose width grows in time. The key result is ⟨x²⟩ = 2Dt: mean squared displacement is proportional to t, not t². Diffusion is slower than ballistic motion — a consequence of the random-walk mechanism where forward and backward steps partially cancel.

The diffusion coefficient D is not a universal constant — it depends on what is diffusing and in what medium. For a gas, kinetic theory gives D ∝ T^(3/2)/p: faster molecules (higher T) and fewer collisions (lower p) mean faster diffusion. For a spherical particle in a liquid, the Stokes-Einstein equation gives D = kT/(6πηr), where η is viscosity and r is the particle radius. This equation has a remarkable practical use: measuring D by tracking particle motion (e.g., in dynamic light scattering) lets you infer the particle's radius — a standard technique for sizing proteins and nanoparticles.

Finally, do not fall into the trap of thinking Fick's laws are only for gases. They describe diffusion in any medium — liquids, solids, and biological membranes — and are foundational to understanding everything from drug delivery kinetics to oxygen transport in tissue to heat conduction (which obeys an identical mathematical form).

Practice Questions 3 questions

Prerequisite Chain

Counting to 10Counting to 20Understanding ZeroThe Number ZeroCounting to FiveOne-to-One CorrespondenceCombining Small Groups Within 5Addition Within 10Addition Within 20Two-Digit Addition Without RegroupingTwo-Digit Addition with RegroupingAddition Within 100Repeated Addition as MultiplicationMultiplication Facts Within 100Division as Equal SharingDivision as Grouping (Measurement Division)Division: Grouping (Repeated Subtraction) ModelDivision: Fair Sharing ModelDivision as Equal SharingDivision as GroupingBasic Division FactsDivision Facts Within 100Two-Digit by One-Digit DivisionDivision with RemaindersRemainders and Quotients in DivisionDivision Word ProblemsIntroduction to Long DivisionFactors and MultiplesPrime and Composite NumbersEquivalent FractionsRelating Fractions and DecimalsDecimal Place ValueReading and Writing DecimalsComparing and Ordering DecimalsAdding and Subtracting DecimalsMultiplying DecimalsDividing DecimalsDividing FractionsMixed Number ArithmeticOrder of 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EnthalpyHeat Capacity and CalorimetryEntropy and Molecular DisorderSpontaneity and ΔGEntropy and Gibbs Free EnergyChemical EquilibriumStatistical Mechanics: Ensembles and the Boltzmann DistributionIntermolecular Potential Energy ModelsTransport Properties of GasesDiffusion and Fick's Laws

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