Entropy phase transitions

Basic thermodynamics, statisticai thermodynamics, third-iaw entropies, phase transitions, mixtures and soiutions, eiectrochemicai systems, surfaces, gravitation, eiectrostatic and magnetic fieids. (in some ways the 3rd and 4th editions (1957 and 1960) are preferabie, being iess idiosyncratic.)... 

Lynden-Bell RM (1995) Landau free energy, Landau entropy, phase transitions and limits of metastability in an analytical model with a variable number of degrees of freedom. Mol. Phys. 86 1353-1374... 

Phase transitions at which the entropy and enthalpy are discontinuous are called first-order transitions because it is the first derivatives of the free energy that are disconthuious. (The molar volume V= (d(i/d p) j is also discontinuous.) Phase transitions at which these derivatives are continuous but second derivatives of G... 

A general expression for the entropy of a system, involving any phase transitions, is... 

Figure 4.3 Behavior of thermodynamic variables at T for an idealized phase transition (a) Gibbs free energy and (b) entropy and volume.

The entropy change AS/ - and the volume change AV/ - are the changes which occur when a unit amount of a pure chemical species is transferred from phase I to phase v at constant temperature and pressure. Integration of Eq. (4-18) for this change yields the latent heat of phase transition ... 

The transition from a ferromagnetic to a paramagnetic state is normally considered to be a classic second-order phase transition that is, there are no discontinuous changes in volume V or entropy S, but there are discontinuous changes in the volumetric thermal expansion compressibility k, and specific heat Cp. The relation among the variables changing at the transition is given by the Ehrenfest relations. 

Observe how in each of these four events, H is zero until, at some critical Ac (which is different for different cases), H abruptly jumps to some higher value and thereafter proceeds relatively smoothly to its final maximum value i max = log2(8) = 3 at A = 7/8. In statistical physics, such abrupt, discontinuous changes in entropy are representative of first-order phase transitions. Interestingly, an examination of a large number of such transition events reveals that there is a small percentage of smooth transitions, which are associated with a second-order phase transition [li90a]. 

It would appear that the tradeoffs between these two requirements are optimized at the phase transition. Langton also cites a very similar relationship found by Crutchfield [crutch90] between a measure of machine complexity and the (per-symbol) entropy for the logistic map. The fact that the complexity/entropy relationship is so similar between two different classes of dynamical systems in turn suggests that what we are observing may be of fundamental importance complexity generically increases with randomness up until a phase transition is reached, beyond which further increases in randomness decrease complexity. We will have many occasions to return to this basic idea. 

Numerical simulations of the k = oo case reveal a sharp phase transition at Ac = 0.27 [wootters]. Simulations also suggest that the spread in values of entropy decreases with increasing k, and that the width of the transition region probably goes as k f [woot90]. 

As indicated earlier, when phase transitions occur, AS for the phase transition must be included in the Third Law calculation of the entropy. For example, Figure 4.4 summarizes the heat capacity of Nt as a function of temperature, up... 

Figure 4.7 Heat capacity and phase transitions in phosphine. The same entropy at point (a) is obtained by going the stable (lower) route or by going the metastable (upper) route. Point (b) is the normal boiling temperature.

Experience indicates that the Third Law of Thermodynamics not only predicts that So — 0, but produces a potential to drive a substance to zero entropy at 0 Kelvin. Cooling a gas causes it to successively become more ordered. Phase changes to liquid and solid increase the order. Cooling through equilibrium solid phase transitions invariably results in evolution of heat and a decrease in entropy. A number of solids are disordered at higher temperatures, but the disorder decreases with cooling until perfect order is obtained. Exceptions are... 

If a phase transition takes place between T = 0 and the temperature of interest, then we also have to include the corresponding entropy of transition by using Eq. 5 and possibly Eq. 4 (Fig. 7.12). For instance, if we want to know the entropy of... 

The semiconducting properties of the compounds of the SbSI type (see Table XXVIII) were predicted by Mooser and Pearson in 1958 228). They were first confirmed for SbSI, for which photoconductivity was found in 1960 243). The breakthrough was the observation of fer-roelectricity in this material 117) and other SbSI type compounds 244 see Table XXIX), in addition to phase transitions 184), nonlinear optical behavior 156), piezoelectric behavior 44), and electromechanical 183) and other properties. These photoconductors exhibit abnormally large temperature-coefficients for their band gaps they are strongly piezoelectric. Some are ferroelectric (see Table XXIX). They have anomalous electrooptic and optomechanical properties, namely, elongation or contraction under illumination. As already mentioned, these fields cannot be treated in any detail in this review for those interested in ferroelectricity, review articles 224, 352) are mentioned. The heat capacity of SbSI has been measured from - 180 to -l- 40°C and, from these data, the excess entropy of the ferro-paraelectric transition... 

For higher diamondoids very limited data are available in the literature. For triamantane, for example, the enthalpy and entropy of transition from crystalline phase II to crystalline phase I are reported [31] as follows ... 

When the free enthalpy of reaction AG for the transformation of the structure of a compound to any other structure is positive, then this structure is thermodynamically stable. Since AG depends on the transition enthalpy AH and the transition entropy AS, and AH and AS in turn depend on pressure and temperature, a structure can be stable only within a certain range of pressures and temperatures. By variation of the pressure and/or the temperature, AG will eventually become negative relative to some other structure and a phase transition will occur. This may be a phase transition from a solid to another solid modification, or it may be a transition to another aggregate state. 

In a second-order phase transition, volume and entropy experience a continuous variation, but at least one of the second derivatives of G exhibits a discontinuity ... 

Cp is the specific heat at constant pressure, k is the compressibility at constant temperature. The conversion process of a second-order phase transition can extend over a certain temperature range. If it is linked with a change of the structure (which usually is the case), this is a continuous structural change. There is no hysteresis and no metastable phases occur. A transformation that almost proceeds in a second-order manner (very small discontinuity of volume or entropy) is sometimes called weakly first order . 

From Eq. (6) it clearly can be seen that pressure and temperature are related by the changes in entropy and volume for the phase change. This equation also shows that once temperature is chosen, pressure must be fixed accordingly. It is easy to show that the change in entropy for the phase transition is simply the... 

Usually the discussion of the ODT of highly asymmetric block copolymers in the strong segregation limit starts from a body-centred cubic (bcc) array of the minority phase. Phase transitions were calculated using SOFT accounting for both the translational entropy of the micelles in a disordered micelle regime and the intermicelle free energy [129]. Results indicate that the ODT occurs between ordered bcc spheres and disordered micelles. 

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