Discontinuous phase transition

In general there are two types of phase transitions, discontinuous and continuous (sometimes called first order and second order respectively). In order to imderstand the difference a brief mention of the thermodynamics of phase transitions is necessary. The Gibbs free energy (G) is defined as... 

One suggested way [55, 56] to compare different experimental probes of phase transition order is to express the phase transition discontinuity in terms of the dimensionless quantity t = - T )/T, where T na is the equilibrium NA... 

The quantitative analysis of phase transitions makes explicit use of the thermodynamic limit and is thus not directly transferable to small systems. Usually, two types of phase transitions are distinguished. As an example, let us consider temperature-driven phase transitions, Discontinuous or first-order transitions refer to the discontinuity of the entropy as a function of temperature ... 

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... 

For both first-order and continuous phase transitions, finite size shifts the transition and rounds it in some way. The shift for first-order transitions arises, crudely, because the chemical potential, like most other properties, has a finite-size correction p(A)-p(oo) C (l/A). An approximate expression for this was derived by Siepmann et al [134]. Therefore, the line of intersection of two chemical potential surfaces Pj(T,P) and pjj T,P) will shift, in general, by an amount 0 IN). The rounding is expected because the partition fiinction only has singularities (and hence produces discontinuous or divergent properties) in tlie limit i—>oo otherwise, it is analytic, so for finite Vthe discontinuities must be smoothed out in some way. The shift for continuous transitions arises because the transition happens when L for the finite system, but when i oo m the infinite system. The rounding happens for the same reason as it does for first-order phase transitions whatever the nature of the divergence in thennodynamic properties (described, typically, by critical exponents) it will be limited by the finite size of the system. 

Figure 4.3b is a schematic representation of the behavior of S and V in the vicinity of T . Although both the crystal and liquid phases have the same value of G at T , this is not the case for S and V (or for the enthalpy H). Since these latter variables can be written as first derivatives of G and show discontinuities at the transition point, the fusion process is called a first-order transition. Vaporization and other familiar phase transitions are also first-order transitions. The behavior of V at Tg in Fig. 4.1 shows that the glass transition is not a first-order transition. One of the objectives of this chapter is to gain a better understanding of what else it might be. We shall return to this in Sec. 4.8. 

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. 

FIG. 4 Qualitative phase diagram close to a first-order irreversible phase transition. The solid line shows the dependence of the coverage of A species ( a) on the partial pressure (Ta). Just at the critical point F2a one has a discontinuity in (dashed line) which indicates coexistence between a reactive state with no large A clusters and an A rich phase (hkely a large A cluster). The dotted fine shows a metastability loop where Fas and F s are the upper and lower spinodal points, respectively. Between F2A and Fas the reactive state is unstable and is displaced by the A rich phase. In contrast, between F s and F2A the reactive state displaces the A rich phase. 

E. V. Albano. On the universality classes of the discontinuous irreversible phase transitions of a multicomponent reaction system. J Phys A (Math Gen) 27 3751-3758, 1994. 

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]. 

We are all familiar with the gas-liquid phase transition undergone by water. In such a transition, a plot of density versus temperature shows a distinct discontinuity at the critical temperature marking the transition point. There are many other common examples of similar phase transitions. 

Table 7.3 lists the four rules in this minimally-diluted rule-family, along with their corresponding iterative maps. Notice that since rules R, R2 and R3 do not have a linear term, / (p = 0) = 0 and mean-field-theory predicts a first-order phase transition. By first order we mean that the phase transition is discontinuous there is an abrupt, discontinuous change at a well defined critical probability Pc, at which the system suddenly goes from having poo = 0 as the only stable fixed point to having an asymptotic density Poo 7 0 as the only stable fixed point (see below). 

An alloy is said to be of Type II if neither the AC nor the BC component has the structure a as its stable crystal form at the temperature range T]. Instead, another phase (P) is stable at T, whereas the a-phase does exist in the phase diagram of the constituents at some different temperature range. It then appears that the alloy environment stabilizes the high-temperature phase of the constituent binary systems. Type II alloys exhibit a a P phase transition at some critical composition Xc, which generally depends on the preparation conditions and temperature. Correspondingly, the alloy properties (e.g., lattice constant, band gaps) often show a derivative discontinuity at Xc. 

It had been discovered long ago that the character of conduction in Agl changes drastically at temperatures above 147°C, when (I- and I -Agl change into a-Agl. At the phase transition temperature the conductivity, o, increases discontinuously by almost four orders of magnitude (from 10 to 1 S/cm). At temperatures above 147°C, the activation energy is very low and the conductivity increases little with temperature, in contrast to its behavior at lower temperatures (see Fig. 8.2). 

Definition A phase transition is an event which entails a discontinuous (sudden) change of at least one property of a material. 

Generally, a phase transition is triggered by an external stress which most commonly is a change in temperature or pressure. Properties that can change discontinuously include volume, density, specific heat, elasticity, compressibility, viscosity, color, electric conductivity, magnetism and solubility. As a rule, albeit not always, phase transitions involve structural changes. Therefore, a phase transition in the solid state normally involves a change from one to another modification. 

If one of these quantities experiences a discontinuous change, i.e. if AS 0 or AV 0, then the phase transition is called a first-order transition according to Ehrenfest. It is accompanied by the exchange of conversion enthalpy AH = TAS with the surroundings. 

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 . 

MnAs exhibits this behavior. It has the NiAs structure at temperatures exceeding 125 °C. When cooled, a second-order phase transition takes place at 125 °C, resulting in the MnP type (cf. Fig. 18.4, p. 218). This is a normal behavior, as shown by many other substances. Unusual, however, is the reappearance of the higher symmetrical NiAs structure at lower temperatures after a second phase transition has taken place at 45 °C. This second transformation is of first order, with a discontinuous volume change AV and with enthalpy of transformation AH. In addition, a reorientation of the electronic spins occurs from a low-spin to a high-spin state. The high-spin structure (< 45°C) is ferromagnetic,... 

As a result, there will be a continuous change in G as the transition of one phase into another takes place. However, for some phase transitions (known as first-order transitions), it is found that there is a discontinuity in the first derivative of G with respect to pressure or temperature. It can be shown that the partial derivative of G with pressure is the equal to volume, and the derivative with respect to temperature is equal to entropy. Therefore, we can express these relationships as follows ... 

A different type of phase transition is known in which there is a discontinuity in the second derivative of free energy. Such transitions are known as second-order transitions. From thermodynamics we know that the change in volume with pressure at constant temperature is the coefficient of compressibility, /3, and the change in volume with temperature at constant pressure is the coefficient of thermal expansion, a. The thermodynamic relationships can be shown as follows ... 

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