Origin of diffusion. In a material near local thermal equilibrium, microscopic carriers transfer energy from hotter regions to colder regions. On distances long compared with their mean free path and times long compared with relaxation times, the local constitutive law is Fourier's law,Combining this temperature-gradient-driven flux with local conservation of energy produces a diffusion equation. This description assumes diffusive thermal conduction; it is not generally valid for ballistic transport, and flow would add advective transport.
Energy balance with heating. Choose any fixed volume , let be its uniform volumetric heat capacity and its heat generation rate per unit volume. The rate of increase of internal energy equals heat generation minus outward heat flux:Since is arbitrary, for constant thermal conductivityThe ratio is the thermal diffusivity in . Here is in , in and in , so both right-hand terms have units . If thermal conductivity varies with position or temperature, the divergence must be retained rather than replacing it by .
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