Generalized Non-equilibrium Heat and Work and the Fate of the Clausius Inequality

Abstract: By generalizing the traditional concept of heat dQ and work dW to also include their time-dependent irreversible components d_{i}Q and d_{i}W allows us to express them in terms of the instantaneous internal temperature T(t) and pressure P(t), whereas the conventional form uses the constant values T_{0} and P_{0} of the medium. This results in an extremely useful formulation of non-equilibrium thermodynamics so that the first law turns into the Gibbs fundamental relation and the Clausius inequality becomes an equality \ointdQ(t)/T(t)\equiv0 in all cases, a quite remarkable but unexpected result. We determine the irreversible components d_{i}Q\equivd_{i}W and discuss how they can be determined to obtain the generalized dW(t) and dQ(t).