Thermodynamic Inequalities in Continuum Mechanics

The constitutive relations for the transport of heat, stress,electric charge, etc., in a continuum must be chosen so thatthe second law of thermodynamics is not violated; the constraintstake the form of inequalities, typically requiring the entropygenerated within a material element to be non-negative. Thepaper is concerned with this concept—its history, thephysical principles on which it depends, how to apply it whensecond-order or non-linear effects are important and how itis widely misused in modern continuum mechanics. The history is reduced to the contributions of five leadingthermodynamicists—Clausius, Maxwell, Gibbs, Boltzmannand Duhem. The object here was to try to discover which formof the inequality one should regard as being fundamental. Oneimportant conclusion is that entropy S must be defined simultaneouslywith the identification of the inequality, and that in generalthis cannot be done until the constitutive equations are known.The empirical element enters with the notion of irreversibility,which is given a precise meaning with the aid of the motionreversed parity (x), a variable x having = +1 or = –1if, when time and motions are reversed, x x or x –x.The macroscopic parity of x, _*(x), is obtained by first replacingx by the constitutive equation for x. The entropy production rate has both irreversible (f) and reversible(r) parts. It is shown that the reciprocal relations followfrom the requirement that the macroscopic parity of (i) mustbe +1. Continuum thermodynamics is based on various principles extractedfrom theory developed for uniform systems, the example chosento illustrate the ideas being the simple monatomic gas. Second-orderconstitutive relations are introduced, and the expressions forentropy and its production rate per unit volume, , obtained.It is shown that the stability condition 0 cannot, in general,be satisfied merely by imposing constraints on the constitutiverelations. To second-order = ₁ + ₂, where ₁ is the usual bilinearform, and the terms in ₂ have an additional derivative. Thesecond-order term ₂ can have both signs, and is not dissipative.The relation between this fact and the frame-dependence of constitutiverelations is explained. The final section illustrates the errors frequently found inthe thermodynamic arguments appearing in books and papers onrational continuum mechanics. The principle of these is that 0 is interpreted as being a constraint on the constitutiverelations alone. Another is the idea that the balance equationscan be set aside as constraints by regarding them as mere definitionsof a heat source and a body force, an error based partly onthe misconception that constitutive relations should be frame-indifferent.Finally, an inequality due to Glansdorff & Prigogine isexamined and found to be in error.