New Phase

These derivatives are based on the ternary compounds of the type M2Si5Ng, where M = Ba, Sr, Ca). To the present author s knowledge, the exact extent of the solid 

---

This region has been divided into two subphases, L and S. The L phase differs from the L2 phase in the direction of tilt. Molecules tilt toward their nearest neighbors in L2 and toward next nearest neighbors in L (a smectic F phase). The S phase comprises the higher-ir and lower-T part of L2. This phase is characterized by smectic H or a tilted herringbone structure and there are two molecules (of different orientation) in the unit cell. Another phase having a different tilt direction, L, can appear between the L2 and L 2 phases. A new phase has been identified in the L 2 domain. It is probably a smectic L structure of different azimuthal tilt than L2 [185]. 

The reports were that water condensed from the vapor phase into 10-100-/im quartz or pyrex capillaries had physical properties distinctly different from those of bulk liquid water. Confirmations came from a variety of laboratories around the world (see the August 1971 issue of Journal of Colloid Interface Science), and it was proposed that a new phase of water had been found many called this water polywater rather than the original Deijaguin term, anomalous water. There were confirming theoretical calculations (see Refs. 121, 122) Eventually, however, it was determined that the micro-amoimts of water that could be isolated from small capillaries was always contaminated by salts and other impurities leached from the walls. The nonexistence of anomalous or poly water as a new, pure phase of water was acknowledged in 1974 by Deijaguin and co-workers [123]. There is a mass of fascinating anecdotal history omitted here for lack of space but told very well by Frank [124]. 

Small metal clusters are also of interest because of their importance in catalysis. Despite the fact that small clusters should consist of mostly surface atoms, measurement of the photon ionization threshold for Hg clusters suggest that a transition from van der Waals to metallic properties occurs in the range of 20-70 atoms per cluster [88] and near-bulk magnetic properties are expected for Ni, Pd, and Pt clusters of only 13 atoms [89] Theoretical calculations on Sin and other semiconductors predict that the stmcture reflects the bulk lattice for 1000 atoms but the bulk electronic wave functions are not obtained [90]. Bartell and co-workers [91] study beams of molecular clusters with electron dirfraction and molecular dynamics simulations and find new phases not observed in the bulk. Bulk models appear to be valid for their clusters of several thousand atoms (see Section IX-3). 

The kinetics of reactions in which a new phase is formed may be complicated by the interference of that phase with the ease of access of the reactants to each other. This is the situation in corrosion and tarnishing reactions. Thus in the corrosion of a metal by oxygen the increasingly thick coating of oxide that builds up may offer more and more impedance to the reaction. Typical rate expressions are the logarithmic law,... 

Bartell and co-workers have made significant progress by combining electron diffraction studies from beams of molecular clusters with molecular dynamics simulations [14, 51, 52]. Due to their small volumes, deep supercoolings can be attained in cluster beams however, the temperature is not easily controlled. The rapid nucleation that ensues can produce new phases not observed in the bulk [14]. Despite the concern about the appropriateness of the classic model for small clusters, its application appears to be valid in several cases [51]. 

The oriented overgrowth of a crystalline phase on the surface of a substrate that is also crystalline is called epitaxial growth [104]. Usually it is required that the lattices of the two crystalline phases match, and it can be a rather complicated process [105]. Some new applications enlist amorphous substrates or grow new phases on a surface with a rather poor lattice match. 

A homogeneous metastable phase is always stable with respect to the fonnation of infinitesimal droplets, provided the surface tension a is positive. Between this extreme and the other thennodynamic equilibrium state, which is inhomogeneous and consists of two coexisting phases, a critical size droplet state exists, which is in unstable equilibrium. In the classical theory, one makes the capillarity approxunation the critical droplet is assumed homogeneous up to the boundary separating it from the metastable background and is assumed to be the same as the new phase in the bulk. Then the work of fonnation W R) of such a droplet of arbitrary radius R is the sum of the... 

Katz A I, Schiferl D and Mills R L 1981 New phases and chemical reactions in solid carbon monoxide under pressure J. Phys. Chem. 88 3176... 

The first and second terras contain phase factors identical to those previously met in Eq. (82). The last term has the new phase factor [Though the power of q in the second term is different from that in Eq. (82), this term enters with a physics-based coefficient that is independent of k in Eq. (82), and can be taken for the present illustration as zero. The full expression is shown in Eq. (86) and the implications of higher powers of q are discussed thereafter.] Then a new off-diagonal matrix element enlarged with the third temi only, multiplied by a (new) coefficient X, is... 

The process by which a solute is transferred from one phase to a new phase. 

The term alumina hydrates or hydrated aluminas is used in industry and commerce to designate aluminum hydroxides. These compounds are tme hydroxides and do not contain water of hydration. Several forms are known a general classification is shown in Figure 1. The most weU-defined crystalline forms ate the trihydroxides, Al(OH) gibbsite [14762-49-3], bayerite [20257-20-9], and nordstrandite [13840-05-6], In addition, two aluminum oxide—hydroxides, AIO(OH), boelimite [1318-23-6] and diaspote [14457-84-2], have been clearly defined. The existence of several other forms of aluminum hydroxides have been claimed. However, there is controversy as to whether they ate truly new phases or stmctures having distorted lattices containing adsorbed or intedameUar water and impurities. 

The manganous ion [16397-91 -4] in solution then reacts with higher valent manganese oxide and zinc ions in solution to form a new phase called... 

The chemistry of the Li—FeS2 system is quite complex. There are at least two steps to the reaction at low discharge rates. The first reaction is an approximately two-electron reduction to a new phase which is a hthiated FeS2 compound. 

The catalytic effect of solid particles (as ia heterogeneous nucleation) is to reduce the energy barrier to formation of a new phase. This, in effect, can reduce the interfacial energy O significantly. 

The design of a plate tower for gas-absorption or gas-stripping operations involves many of the same principles employed in distillation calculations, such as the determination of the number of theoretical plates needed to achieve a specified composition change (see Sec. 13). Distillation differs from gas absorption in that it involves the separation of components based on the distribution of the various substances between a gas phase and a hquid phase when all the components are present in Doth phases. In distillation, the new phase is generated From the original feed mixture by vaporization or condensation of the volatile components, and the separation is achieved by introducing reflux to the top of the tower. 

In gas absorption, the new phase consists of an inert nonvolatile solvent (absorption) or an inert nonsoluble gas (stripping), and normally no reflux is involved. The following paragraphs discuss some of the considerations peculiar to gas-absorption calculations for plate towers and some of the approximate design methods that can be employed when simplifying assumptions are vahd. 

Advantages to Membrane Separation This subsertion covers the commercially important membrane applications. AU except electrodialysis are pressure driven. All except pervaporation involve no phase change. All tend to be inherently low-energy consumers in the-oiy if not in practice. They operate by a different mechanism than do other separation methods, so they have a unique profile of strengths and weaknesses. In some cases they provide unusual sharpness of separation, but in most cases they perform a separation at lower cost, provide more valuable products, and do so with fewer undesirable side effects than older separations methods. The membrane interposes a new phase between feed and product. It controls the transfer of mass between feed and product. It is a kinetic, not an equihbrium process. In a separation, a membrane will be selective because it passes some components much more rapidly than others. Many membranes are veiy selective. Membrane separations are often simpler than the alternatives. 

For many years, it was thought that the macro solute forms a new phase near the membrane—that of a gel or gel-like layer. The model provided good correlations of experimental data and has been widely used. It does not fit known experimental facts. An explanation that fits the known data well is based on osmotic pressure. The van t Hoff equation [Eq. (22-75)] is hopelessly inadequate to predict the osmotic pressure of a macromolecular solution. Using the empirical expression... 

Another important property is alloy structural stability. This means freedom from formation of new phases or drastic rearrangement of those originally present within the metal structure as a result of thermal experience. Such changes may have a detrimental effect upon strength or corrosion resistance or both. 

Figure 1.11 The formation of metal clusters during the nucleation of a new phase. The co-ordination is first tetrahedral, leading to 5-fold symmetry, until the 13-atom icosahedron is formed which transforms into the cubic icosahedron of the stable phase...

The kinetics of spinodal decomposition is complicated by the fact that the new phases which are formed must have different molar volumes from one another, and so tire interfacial energy plays a role in the rate of decomposition. Anotlrer important consideration is that the transformation must involve the appearance of concenuation gradients in the alloy, and drerefore the analysis above is incorrect if it is assumed that phase separation occurs to yield equilibrium phases of constant composition. An example of a binary alloy which shows this feature is the gold-nickel system, which begins to decompose below 810°C. 

We saw in Chapter 6 that diffusive transformations (like the growth of metal crystals from the liquid during solidification, or the growth of one solid phase at the expense of another during a polymorphic change) involve a mechanism in which atoms are attached to the surfaces of the growing crystals. This means that diffusive transformations can only take place if crystals of the new phase are already present. But how do these crystals - or nuclei - form in the first place ... 

Nucleation in solids is very similar to nucleation in liquids. Because solids usually contain high-energy defects (like dislocations, grain boundaries and surfaces) new phases usually nucleate heterogeneously homogeneous nucleation, which occurs in defect-free regions, is rare. Figure 7.5 summarises the various ways in which nucleation can take place in a typical polycrystalline solid and Problems 7.2 and 7.3 illustrate how nucleation theory can be applied to a solid-state situation. 

In this chapter we have shown that diffusive transformations can only take place if nuclei of the new phase can form to begin with. Nuclei form because random atomic vibrations are continually making tiny crystals of the new phase and if the temperature is low enough these tiny crystals are thermodynamically stable and will grow. In homogeneous nucleation the nuclei form as spheres within the bulk of the material. In... 

Fig. 8.7. The displacive f.c.c. —> b.c.c. transformation in iron. B.c.c. lenses nucleate at f.c.c. groin boundaries and grow almost instantaneously. The lenses stop growing when they hit the next grain boundary. Note that, when a new phase in any material is produced by o displacive transformation it is always referred to os "martensite". Displacive transformations ore often called "martensitic" transformations os o result.

---