Phase transitions thermodynamic representation

Thermodynamic representation of transitions often represents a challenge. First-order phase transitions are more easily handled numerically than second-order transitions. The enthalpy and entropy of first-order phase transitions can be calculated at any temperature using the heat capacity of the two phases and the enthalpy and entropy of transition at the equilibrium transition temperature. Small pre-tran-sitional contributions to the heat capacity, often observed experimentally, are most often not included in the polynomial representations since the contribution to the... 

In Fig. 3 c the schematic volume-temperature curve of a non crystallizing polymer is shown. The bend in the V(T) curve at the glass transition indicates, that the extensive thermodynamic functions, like volume V, enthalpy H and entropy S show (in an idealized representation) a break. Consequently the first derivatives of these functions, i.e. the isobaric specific volume expansion coefficient a, the isothermal specific compressibility X, and the specific heat at constant pressure c, have a jump at this point, if the curves are drawn in an idealized form. This observation of breaks for the thermodynamic functions V, H and S in past led to the conclusion that there must be an internal phase transition, which could be a true thermodynamic transformation of the second or higher order. In contrast to this statement, most authors... 

Fig. 24. The electronic and thermodynamic phase transitions at the nonmetal-to-metal transition a schematic representation of the free energy of a metal-ammonia solution in the temperature range of the miscibility gap, showing the NM-M transition as a function of metal concentration for increasing temperatures.

The subscripts i and j refer to products and reactants respectively, and L represents the latent heats of transition. Equation H. B. 2. is easily developed from the diagramatic representation in figure n. B. 1., which for convenience omits phase transitions. According to the first law of thermodynamics the heat changes in going from reactants at temperature T0 to products at temperature Tp by either Path A or Path B shown must be the same. Path A raises the reactants from temperature T0 to Tt, and reacts at Tx. Path B reacts at T0 and raises the products from T0 to Tx. Thus ... 

Another aspect of lattice models concerns the determination of phase behavior. As far as continuous models were concerned we emphasized already that an investigation of phase transitions in such models usually requires a mechanical representation of the relevant thermod3marnic potential in terms of one or more elements of the micrascopic stre.ss teusor. The existence of sucli a mechanical representation was linked inevitably to symmetry considerations in Section 1.6, where it was also pointed out that such a mechanical expression may not exist at all. In this case a determination of the thermodynamic potential requires thermodynamic integration along some suitable path in thermodynamic state space, which may turn out to be computationally demanding. 

Phase transitions with the appearance of a spontaneous symmetry breaking are characterised by order parameters. In the spirit of Landau theory they belong to representations of the high temperature symmetry group and also characterise the class of remaining symmetries in the low-temperature phase. Furthermore they partly determine the type of possible excitations in the ordered phase which in turn influence the low-temperature thermodynamic and transport properties. The investigation of the order parameter symmetry is therefore of singular... 

One should thus not regard LCEs as entirely below-critical or above-critical systems, but rather as systems in which both types of phase-transition behaviours may be found, the extent of which is determined by the values of (G) and Gg- We shall introduce the term smeared criticality for such behaviour. In Fig. 16a, the graphical representation illustrates the extent of each type of phase transition behaviour in two LCEs, one prevalently below critical and the other prevalently above critical. A straightforward manifestation of the smeared criticality is the presence of latent heat in many LCE systems that exhibit a supercritical, effective thermodynamic response (see Sect. 5). This latent heat is released by the below-critical component of the LCE whose extent is given by the surface of the shaded area in Fig. 16. 

Fig. 1.5 Schematic representation of the evolution of life from its precursors, on the basis of the definition of life given by the authors. If bioenergetic mechanisms have developed via autonomous systems, the thermodynamic basis for the beginning of the archiving of information, and thus for a one-polymer world such as the RNA world , has been set up. Several models for this transition have been discussed. This phase of development is possibly the starting point for the process of Darwinian evolution (with reproduction, variation and heredity), but still without any separation between genotype and phenotype. According to the authors definition, life begins in exactly that moment when the genetic code comes into play, i.e., in the transition from a one-polymer world to a two-polymer world . The last phase, open-ended evolution, then follows. After Ruiz-Mirazo et al. (2004)...

The liquid crystal melt, which comes into being at the glass-rubber transition or at the crystal-melt transition, may have several phase states (Mesophases) one or more smectic melt phases, a nematic phase and sometimes a chiral or cholesteric phase the final phase will be the isotropic liquid phase, if no previous decomposition takes place. All mesophase transitions are thermodynamically real first order effects, in contradistinction to the glass-rubber transition. A schematic representation of some characteristic liquid crystal phase structures is shown in Fig. 6.13, where also so-called columnar phases formed from disclike molecules is given. 

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