Definition of diffusion flux Each model of diffusion expresses the
diffusion flux with the use of concentrations, densities and their derivatives. Flux is a vector \mathbf{J} representing the quantity and direction of transfer. Given a small
area \Delta S with normal \boldsymbol{\nu}, the transfer of a
physical quantity N through the area \Delta S per time \Delta t is :\Delta N = (\mathbf{J},\boldsymbol{\nu}) \,\Delta S \,\Delta t +o(\Delta S \,\Delta t)\, , where (\mathbf{J},\boldsymbol{\nu}) is the
inner product and o(\cdots) is the
little-o notation. If we use the notation of
vector area \Delta \mathbf{S}=\boldsymbol{\nu} \, \Delta S then :\Delta N = (\mathbf{J}, \Delta \mathbf{S}) \, \Delta t +o(\Delta \mathbf{S} \,\Delta t)\, . The
dimension of the diffusion flux is [flux] = [quantity]/([time]·[area]). The diffusing physical quantity N may be the number of particles, mass, energy, electric charge, or any other scalar
extensive quantity. For its density, n, the diffusion equation has the form :\frac{\partial n}{\partial t}= - \nabla \cdot \mathbf{J} +W \, , where W is intensity of any local source of this quantity (for example, the rate of a chemical reaction). For the diffusion equation, the
no-flux boundary conditions can be formulated as (\mathbf{J}(x),\boldsymbol{\nu}(x))=0 on the boundary, where \boldsymbol{\nu} is the normal to the boundary at point x.
Normal single component concentration gradient Fick's first law: The diffusion flux, \mathbf{J}, is proportional to the negative gradient of spatial concentration, n(x,t): :\mathbf{J}=-D(x) \,\nabla n(x,t), where
D is the
diffusion coefficient, which can be estimated for a given mixture using, for example, the empirical Vignes correlation model or the physically motivated entropy scaling. The corresponding
diffusion equation (Fick's second law) is :\frac{\partial n(x,t)}{\partial t}=\nabla\cdot( D(x) \,\nabla n(x,t))\, . In case the diffusion coefficient is independent of x, Fick's second law can be simplified to :\frac{\partial n(x,t)}{\partial t}=D \, \Delta n(x,t)\ , where \Delta is the
Laplace operator, :\Delta n(x,t) = \sum_i \frac{\partial^2 n(x,t)}{\partial x_i^2} \ .
Multicomponent diffusion and thermodiffusion Fick's law describes diffusion of an admixture in a medium. The concentration of this admixture should be small and the gradient of this concentration should be also small. The driving force of diffusion in Fick's law is the antigradient of concentration, -\nabla n. In 1931,
Lars Onsager included the multicomponent transport processes in the general context of linear non-equilibrium thermodynamics. For multi-component transport, :\mathbf{J}_i=\sum_j L_{ij} X_j \, , where \mathbf{J}_i is the flux of the ith physical quantity (component), X_j is the jth
thermodynamic force and L_{ij} is Onsager's matrix of
kinetic transport coefficients. The thermodynamic forces for the transport processes were introduced by Onsager as the space gradients of the derivatives of the
entropy density s (he used the term "force" in quotation marks or "driving force"): :X_i= \nabla \frac {\partial s(n)}{\partial n_i}\, , where n_i are the "thermodynamic coordinates". For the heat and mass transfer one can take n_0=u (the density of
internal energy) and n_i is the concentration of the ith component. The corresponding driving forces are the space vectors : X_0= \nabla \frac{1}{T}\ , \;\;\; X_i= - \nabla \frac{\mu_i}{T} \; (i >0) , because \mathrm{d}s = \frac{1}{T} \,\mathrm{d}u-\sum_{i \geq 1} \frac{\mu_i}{T} \, {\rm d} n_i where
T is the absolute temperature and \mu_i is the chemical potential of the ith component. It should be stressed that the separate diffusion equations describe the mixing or mass transport without bulk motion. Therefore, the terms with variation of the total pressure are neglected. It is possible for diffusion of small admixtures and for small gradients. For the linear Onsager equations, we must take the thermodynamic forces in the
linear approximation near equilibrium: :X_i= \sum_{k \geq 0} \left.\frac{\partial^2 s(n)}{\partial n_i \, \partial n_k}\right|_{n=n^*} \nabla n_k \ , where the derivatives of s are calculated at equilibrium n^*. The matrix of the
kinetic coefficients L_{ij} should be symmetric (
Onsager reciprocal relations) and
positive definite (
for the entropy growth). The transport equations are :\frac{\partial n_i}{\partial t}= - \operatorname{div} \mathbf{J}_i =- \sum_{j\geq 0} L_{ij}\operatorname{div} X_j = \sum_{k\geq 0} \left[-\sum_{j\geq 0} L_{ij} \left.\frac{\partial^2 s(n)}{\partial n_j \, \partial n_k}\right|_{n=n^*}\right] \, \Delta n_k\ . Here, all the indexes are related to the internal energy (0) and various components. The expression in the square brackets is the matrix D_{ik} of the diffusion (
i,
k > 0), thermodiffusion (
i > 0,
k = 0 or
k > 0,
i = 0) and
thermal conductivity () coefficients. Under
isothermal conditions T = constant. The relevant
thermodynamic potential is the free energy (or the
free entropy). The thermodynamic driving forces for the isothermal diffusion are antigradients of chemical potentials, -(1/T)\,\nabla\mu_j, and the matrix of diffusion coefficients is :D_{ik}=\frac{1}{T}\sum_{j\geq 1} L_{ij} \left.\frac{\partial \mu_j(n,T)} { \partial n_k}\right|_{n=n^*} (
i,k > 0). There is intrinsic arbitrariness in the definition of the thermodynamic forces and kinetic coefficients because they are not measurable separately and only their combinations \sum_j L_{ij}X_j can be measured. For example, in the original work of Onsager this multiplier is omitted but the sign of the thermodynamic forces is opposite. All these changes are supplemented by the corresponding changes in the coefficients and do not affect the measurable quantities.
Nondiagonal diffusion must be nonlinear The formalism of linear irreversible thermodynamics (Onsager) generates the systems of linear diffusion equations in the form :\frac{\partial c_i}{\partial t} = \sum_j D_{ij} \, \Delta c_j. If the matrix of diffusion coefficients is diagonal, then this system of equations is just a collection of decoupled Fick's equations for various components. Assume that diffusion is non-diagonal, for example, D_{12} \neq 0, and consider the state with c_2 = \cdots = c_n = 0. At this state, \partial c_2 / \partial t = D_{12} \, \Delta c_1. If D_{12} \, \Delta c_1(x) at some points, then c_2(x) becomes negative at these points in a short time. Therefore, linear non-diagonal diffusion does not preserve positivity of concentrations. Non-diagonal equations of multicomponent diffusion must be non-linear. For charged particles: : D = \frac{\mu \, k_\text{B} T}{q}, where
D is the
diffusion constant,
μ is the "mobility",
kB is the
Boltzmann constant,
T is the
absolute temperature, and
q is the
elementary charge, that is, the charge of one electron. Below, to combine in the same formula the chemical potential
μ and the mobility, we use for mobility the notation \mathfrak{m}.
Diffusion across a membrane The mobility-based approach was further applied by T. Teorell. In 1935, he studied the diffusion of ions through a membrane. He formulated the essence of his approach in the formula: :
the flux is equal to mobility × concentration × force per gram-ion. This is the so-called
Teorell formula. The term "gram-ion" ("gram-particle") is used for a quantity of a substance that contains the
Avogadro number of ions (particles). The common modern term is
mole. The force under isothermal conditions consists of two parts: • Diffusion force caused by concentration gradient: -RT \frac{1}{n} \, \nabla n = -RT \, \nabla (\ln(n/n^\text{eq})). • Electrostatic force caused by electric potential gradient: q \, \nabla \varphi. Here
R is the
gas constant,
T is the absolute temperature,
n is the concentration, the equilibrium concentration is marked by a superscript "eq",
q is the charge and
φ is the electric potential. The simple but crucial difference between the Teorell formula and the Onsager laws is the concentration factor in the Teorell expression for the flux. In the Einstein–Teorell approach, if for the finite force the concentration tends to zero then the flux also tends to zero, whereas the Onsager equations violate this simple and physically obvious rule. The general formulation of the Teorell formula for non-perfect systems under isothermal conditions is :m \frac{d^2x}{dt^2} = -\frac{1}{\mu}\frac{dx}{dt} + F(t) where •
x is the position. •
μ is the mobility of the particle in the fluid or gas, which can be calculated using the
Einstein relation (kinetic theory). •
m is the mass of the particle. •
F is the random force applied to the particle. •
t is time. Solving this equation, one obtained the time-dependent diffusion constant in the long-time limit and when the particle is significantly denser than the surrounding fluid, :\mathbf{J}=- \phi D \,\nabla n^m :\frac{\partial n}{\partial t} = D \, \Delta n^m \, , where
D is the diffusion coefficient, Φ is porosity,
n is the concentration,
m > 0 (usually
m > 1, the case
m = 1 corresponds to Fick's law). Care must be taken to properly account for the porosity (Φ) of the porous medium in both the flux terms and the accumulation terms. For example, as the porosity goes to zero, the molar flux in the porous medium goes to zero for a given concentration gradient. Upon applying the divergence of the flux, the porosity terms cancel out and the second equation above is formed. For diffusion of gases in porous media this equation is the formalization of
Darcy's law: the
volumetric flux of a gas in the porous media is :q=-\frac{k}{\mu}\,\nabla p where
k is the
permeability of the medium,
μ is the
viscosity and
p is the pressure. The advective molar flux is given as
J =
nq and for p \sim n^\gamma Darcy's law gives the equation of diffusion in porous media with
m =
γ + 1. In porous media, the average linear velocity (ν), is related to the volumetric flux as: \upsilon= q/\phi Combining the advective molar flux with the diffusive flux gives the advection dispersion equation \frac{\partial n}{\partial t} = D \, \Delta n^m \ - \nu\cdot \nabla n^m, For underground water infiltration, the
Boussinesq approximation gives the same equation with
m = 2. For plasma with the high level of radiation, the
Zeldovich–Raizer equation gives
m > 4 for the heat transfer. ==Diffusion in physics==