 Clausius–Duhem inequality

The Clausius-Duhem inequality is a local expression of the Second law of thermodynamics for a simple continuum whose thermodynamic entropy flux is heat flux divided by positive absolute temperature. With specific entropy $s$, outward heat flux $\mathbf{q}$ and heat supply $r$ per unit mass, it readsCombining this with the local internal energy balance and writing the specific Helmholtz free energy as $\psi =e-Ts$ givesHere $D$ is the rate-of-strain tensor and the dot denotes a material derivative.^[ref]

The inequality constrains constitutive equations, including both mechanical dissipation and thermal conduction. For Fourier's law $\mathbf{q}=-k\nabla T$ with $k\ge 0$, the thermal contribution is $k|\nabla T{|}^2/T\ge 0$. This direct sign check explains why passive thermal conduction carries heat down a temperature gradient. More general continua can require a different thermodynamic entropy flux, so the stated assumption matters.

The Clausius-Duhem inequality is a fundamental principle in thermodynamics and continuum mechanics that expresses the second law of thermodynamics in a differential form. It serves as a mathematical statement of the irreversibility of thermodynamic processes and the concept of entropy production. In simple terms, the inequality can be stated as follows: \[ \frac{dS}{dt} \geq 0 \] where \( S \) is the entropy of a system.