Evolution of non-equilibrium systems towards equilibrium is governed by the second law of thermodynamics. For example, in the previous section we showed that for an adiabatically isolated system entropy must increase in any spontaneous change and reaches a maximum in equilibrium. What about out of equilibrium systems that are not adiabatically isolated and which may also be subject to external ...

The nonadditive thermodynamic formalism is a generalization of the classical thermodynamic formalism, in which the topological pressure of a single function φ is replaced by the topological pressure of a sequence of functions Φ = (φn)n. The theory also includes a variational principle for the topological pressure, although with restrictive assumptions on Φ. Our main objective is to provide a ne...

Evolution of non-equilibrium systems towards equilibrium is governed by the second law of thermodynamics. For example, in the previous section we showed that for an adia­ batically isolated system entropy must increase in any spontaneous change and reaches a maximum in equilibrium. What about out of equilibrium systems that are not adiabati­ cally isolated and which may also be subject to exter...

We present the results of extensive computer simulations performed on solutions of monodisperse charged rod-like polyelectrolytes in the presence of trivalent counterions. To overcome energy barriers we used a combination of parallel tempering and hybrid Monte Carlo techniques. Our results show that for small values of the electrostatic interaction the solution mostly consists of dispersed sing...

Consider an equilibrium reaction aA+ bB ⇀↽ cC+ dD We do not specify any phases, as we will treat the reaction generally using activities. An equilibrium reaction is one that can proceed in both directions, as indicated by the ⇀↽ symbol replacing the usual −→ in the chemical equation. Recall that the molar free energy ∆Ḡj for compound j in the reaction in terms of its activity aj as ∆Ḡ = ∆Ḡ◦ +RT...

Two phenomenological approaches are currently used in the study of the vitreous state. One is based on the concept of fictive temperature introduced by Tool [J. Res. Natl. Bur. Stand. 34, 199 (1945)] and recently revisited by Nieuwenhuizen [Phys. Rev. Lett. 80, 5580 (1998)]. The other is based on the thermodynamics of irreversible processes initiated by De Donder at the beginning of the last ce...

The wish to determine thermodynamic data of electrochemical reactions and of the involved compounds is one of the most important motivations to perform electrochemical measurements. After calorimetry, electrochemistry is the second most important tool to determine thermodynamic data. Although ab initio quantum chemical calculations can be used for the calculation of thermodynamic data of small ...