Volume changes, phase transitions

Second-order phase transitions, which are quite rare, involve a discontinuity in second derivatives at the transition point. They occur with zero enthalpy, entropy, and volume change. The transitions of certain metals (e.g., Hg and Sn) to a state in which they have no electrical resistance (superconductivity) are second-order phase transitions. 

Consider how the change of a system from a thennodynamic state a to a thennodynamic state (3 could decrease the temperature. (The change in state a —> f3 could be a chemical reaction, a phase transition, or just a change of volume, pressure, magnetic field, etc). Initially assume that a and (3 are always in complete internal equilibrium, i.e. neither has been cooled so rapidly that any disorder is frozen in. Then the Nemst heat... 

Just as one may wish to specify the temperature in a molecular dynamics simulation, so may be desired to maintain the system at a constant pressure. This enables the behavior of the system to be explored as a function of the pressure, enabling one to study phenomer such as the onset of pressure-induced phase transitions. Many experimental measuremen are made under conditions of constant temperature and pressure, and so simulations in tl isothermal-isobaric ensemble are most directly relevant to experimental data. Certai structural rearrangements may be achieved more easily in an isobaric simulation than i a simulation at constant volume. Constant pressure conditions may also be importai when the number of particles in the system changes (as in some of the test particle methoc for calculating free energies and chemical potentials see Section 8.9). 

Besides the chemical composition, porosity is another property of stone which has great influence on its preservation. An increased porosity increases the exposed surface and pores allow movement of materials such as water and its solutes through the stones. If the pores are blocked or reduced in diameter such substances may be trapped within resulting in increased local interior damage. Exposure to the climatic elements is one important source of decay. Freeze-thaw cycles, in particular, result in pressures on the pore walls of the stone s interior from changes in volume during the phase transition... 

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 ... 

Bancroft et al. (1965), and in the case of CaO and the B1 to B2 transition discovered by Jeanloz and Ahrens (1979), complete reversion of the low-pressure phase occurs upon unloading. These latter transitions involve rearrangement of the lattice which can occur via its deformation rather than complete reconstruction. The volume change in the Si02 transition is much larger than in the case of CaO, as seen in Fig. 4.15. In contrast to the pressure-volume plane when plotted in the Ph-u, plane, the occurrence of these transitions is less striking in this representation (Fig. 4.14). 

Fig. 2.12. If solids undergo a shock-induced polymorphic transformation, the volume change at the transformation causes significant changes in the wave profile produced by shock loading. In the figure, is the applied pressure, Pj is the pressure of the phase transition, and HEL is the Hugoniot elastic limit.

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. 

The indicated transition pressure of 15 GPa is in agreement with the published data with shock-wave structure measurements on a 3% silicon-iron alloy, the nominal composition of Silectron. A mixed phase region from 15 to 22.5 GPa appears quite reasonable based on shock pressure-volume data. Thus, the direct measure of magnetization appears to offer a sensitive measure of characteristics of shock-induced, first-order phase transitions involving a change in magnetization. 

A volume change is usually associated with phase transitions in lipid bilayers. 

The parameters which characterize the thermodynamic equilibrium of the gel, viz. the swelling degree, swelling pressure, as well as other characteristics of the gel like the elastic modulus, can be substantially changed due to changes in external conditions, i.e., temperature, composition of the solution, pressure and some other factors. The changes in the state of the gel which are visually observed as volume changes can be both continuous and discontinuous [96], In principle, the latter is a transition between the phases of different concentration of the network polymer one of which corresponds to the swollen gel and the other to the collapsed one. 

Le — latent heat of evaporation. v2 — Vi = Ar = volume change accompanying unit mass of phase transition at the pressure p. 

Minol II will exhibit a reversible phase transition beginning at 32°, producing volume changes of about 3.8%. These volume changes could causfe microcrystalline cracks and pores which could reduce detonation velocity and mechanical strength (Ref 36)... 

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. 

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,... 

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