Clausius–Duhem inequality


The Clausius–Duhem inequality is a way of expressing the second law of thermodynamics that is used in continuum mechanics. This inequality is particularly useful in determining whether the constitutive relation of a material is thermodynamically allowable.
This inequality is a statement concerning the irreversibility of natural processes, especially when energy dissipation is involved. It was named after the German physicist Rudolf Clausius and French physicist Pierre Duhem.

Clausius–Duhem inequality in terms of the specific entropy

The Clausius–Duhem inequality can be expressed in integral form as
In this equation is the time, represents a body and the integration is over the volume of the body, represents the surface of the body, is the mass density of the body, is the specific entropy, is the normal velocity of, is the velocity of particles inside, is the unit normal to the surface, is the heat flux vector, is an energy source per unit mass, and is the absolute temperature. All the variables are functions of a material point at at time.
In differential form the Clausius–Duhem inequality can be written as
where is the time derivative of and is the divergence of the vector.
Proof
Assume that is an arbitrary fixed control volume. Then
and the derivative can be taken inside the integral to give
Using the divergence theorem, we get
Since is arbitrary, we must have
Expanding out
or,
or,
Now, the material time derivatives of and are given by
Therefore,
From the conservation of mass. Hence,

Clausius–Duhem inequality in terms of specific internal energy

The inequality can be expressed in terms of the internal energy as
where is the time derivative of the specific internal energy , is the Cauchy stress, and is the gradient of the velocity. This inequality incorporates the balance of energy and the balance of linear and angular momentum into the expression for the Clausius–Duhem inequality.
Proof
Using the identity
in the Clausius–Duhem inequality, we get
Now, using index notation with respect to a Cartesian coordinate system,
Hence,
From the balance of energy
Therefore,
Rearranging,

Dissipation

The quantity
is called the dissipation which is defined as the rate of internal entropy production per unit volume times the absolute temperature. Hence the Clausius–Duhem inequality is also called the dissipation inequality. In a real material, the dissipation is always greater than zero.
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