Phase-transition behavior

Figure 14 Phase behavior transitions as the concentration of sodium hydroxide is increased in a system containing a fatty acid, oil, and water.

In the previous case the phase behavior transition was produced by a change in the ratio S/A, i.e., in the amphiphilic mixture hydrophilicity. In the present one the phase behavior change is mainly due to the total concentration of amphiphile mixture, which drives a considerable hydrophilicity variation. These are two cases of quaternary systems in which a composition change produces a phase behavior change typical of the fonnulation effect in Winsor s diagrams. Such a... 

FIG. 7 Phase behavior transition and emulsion transitional inversion due to a change in physicochemical formulation. 

An essential component of cell membranes are the lipids, lecithins, or phosphatidylcholines (PC). The typical ir-a behavior shown in Fig. XV-6 is similar to that for the simple fatty-acid monolayers (see Fig. IV-16) and has been modeled theoretically [36]. Branched hydrocarbons tails tend to expand the mono-layer [38], but generally the phase behavior is described by a fluid-gel transition at the plateau [39] and a semicrystalline phase at low a. As illustrated in Fig. XV-7, the areas of the dense phase may initially be highly branched, but they anneal to a circular shape on recompression [40]. The theoretical evaluation of these shape transitions is discussed in Section IV-4F. 

Molecular dynamics simulations have also been used to interpret phase behavior of DNA as a function of temperature. From a series of simulations on a fully solvated DNA hex-amer duplex at temperatures ranging from 20 to 340 K, a glass transition was observed at 220-230 K in the dynamics of the DNA, as reflected in the RMS positional fluctuations of all the DNA atoms [88]. The effect was correlated with the number of hydrogen bonds between DNA and solvent, which had its maximum at the glass transition. Similar transitions have also been found in proteins. 

In some of these models (see Sec. Ill) the surfactants are still treated as flexible chains [24]. This allows one to study the role of the chain length and chain conformations. For example, the chain degrees of freedom are responsible for the internal phase transitions in monolayers and bilayers, in particular the hquid/gel transition. The chain length and chain architecture determine the efficiency of an amphiphile and thus influence the phase behavior. Moreover, they affect the shapes and size distributions of micelles. Chain models are usually fairly universal, in the sense that they can be used to study many different phenomena. 

One prominent example of rods with a soft interaction is Gay-Berne particles. Recently, elastic properties were calculated [89,90]. Using the classical Car-Parrinello scheme, the interactions between charged rods have been considered [91]. Concerning phase transitions, the sohd-fluid equihbria for hard dumbbells that interact additionally with a quadrupolar force was considered [92], as was the nematic-isotropic transition in a fluid of dipolar hard spherocylinders [93]. The influence of an additional attraction on the phase behavior of hard spherocylinders was considered by Bolhuis et al. [94]. The gelation transition typical for clays was found in a system of infinitely thin disks carrying point quadrupoles [95,96]. In confined hquid-crystalline films tilted molecular layers form near each wall [97]. Chakrabarti has found simulation evidence of critical behavior of the isotropic-nematic phase transition in a porous medium [98]. 

Several works have been published about the phase behavior of polybibenzoates, showing the ability of the biphenyl group to produce mesophase structures. Different spacers have been used, and the results show that the structure of the spacer influences very much the transition temperatures and the nature and stability of the mesophases, as well as the ability to generate three-dimensional crystals. 

The effect of lateral methyl groups in the spacer on the phase behavior has been studied in several polybibenzoates [18,19] derived from poly(tetramethy]ene p,p bibenzoate), P4MB. The branched polymers display transition temperatures significantly lower than P4MB. Moreover, the substituents have a clear effect on the kind of mesophase formed. Thus, P4MB displays a smectic A mesophase, while the lateral methyl groups... 

The different phase behaviors are evidenced in the corresponding free energy diagrams, which have been estimated for both polymers [15]. These diagrams are shown in Fig. 10 (due to the different approximations used in the calculation of the free energy differences, these diagrams are only semiquantitative [15]). It can be seen that the monotropic transition of the crystal in... 

The phase behavior of a-ester sulfonates has been studied in detail with methyl laurate and methyl palmitate [58]. In both cases, at higher temperatures, as the surfactant concentration increases, there is a transition from an isotropic solution to a hexagonal liquid crystalline phase and finally, at high surfactant concentrations, to a lamellar liquid crystal (Fig. 4). The crystal/liquid-crys-tal phase transition occurs at even higher temperatures as the chain length increases. On the other hand, chain length has practically no influence on the... 

LeiblerL., Theory of microphase separation in block copolymers. Macromolecules, 13, 1602, 1980. Eoerster S., Khandpur A.K., Zhao J., Bates E.S., Hamley I.W., Ryan A.J., and Bras W. Complex phase behavior of polyisoprene-polystyrene diblock copolymers near the order-disorder transition. Macromolecules, 21, 6922, 1994. 

Major determinants of membrane fluidity may be grouped within two categories [53] (1) intrinsic determinants, i.e., those quantifying the membrane composition and phase behavior, and (2) extrinsic determinants, i.e., environmental factors (Table 1). In general, any manipulation that induces an increase in the molal volume of the lipids, e.g., increase in temperature or increase in the fraction of unsaturated acyl chains, will lead to an increase in membrane fluidity. In addition, several intrinsic and extrinsic factors presented in Table 1 determine the temperature at which the lipid molecules undergo a transition from the gel state to liquid crystalline state, a transition associated with a large increase in bilayer fluidity. 

Phase behavior in complex fluids such as polymer blends and block copolymers has been a rich area of the chemical sciences. Near-critical and other transitional phenomena are frequently prominent. Since molecular movement in viscous systems such as these is comparatively slow, phase transitions can be studied more easily in time, and manipulated by quenching and other external influences. Processes for controlled growth of ordered materials are often readily influenced by diffusion, a variety of external fields, and the influence of interacting boundaries, or flow. 

The phase behavior is changed considerably upon addition of PPDA monomer to the FLC as shown in Figure 2. The reduced transition temperatures for the LC phases, i.e. the transition temperature for the pure FLC subtracted from that of the FLC/monomer (or polymer) mixtures, are plotted as a function of the concentration before and after polymerization. Before polymerization the reduced transition temperatures decrease almost linearly for the first order isotropic to smectic A transition, as would be expected. The reduced temperatures for the transition from the smectic A to the smectic C phase for the monomer/FLC mixtures also decrease linearly with concentration, but the decrease is considerably more pronounced. This decrease continues until the LC is saturated in monomer (about 13 wt%). 

After polymerizing, the phase behavior changes dramatically. The phase transition temperatures return to values very close to those observed in the pure FLC. The interactions which lower the transitions in monomer/FLC systems are not significant in polymer/FLC systems. Similar results are observed in HDDA/FLC systems. The only notable exception is that the monomer saturation concentration occurs at a significantly lower concentration (5 wt%). 

The introduction of a polymer network into an FLC dramatically changes phase and electro-optic behavior. Upon addition of monomer to the FLC, the phase transitions decrease and after polymerization return to values close to that observed in the neat FLC. The phase behavior is similar for the amorphous monomers, HDD A and PPDA. The electro-optic properties, on the other hand, are highly dependent on the monomer used to form the polymer/FLC composite. The ferroelectric polarization decreases for both HDDA and PPDA/FLC systems, but the values for each show extremely different temperature dependence. Further evidence illustrating the different effects of each of the two polymers is found upon examining the polarization as both the temperature and LC phase of polymerization are changed. In PPDA systems the polarization remains fairly independent of the polymerization temperature. On the other hand, the polarization increases steadily as the polymerization temperature of HDDA systems is increased in the ordered LC phases. 

This chapter is designed to show how coordination chemistry may be studied in the gas phase and give some examples from the literature. The examples will mainly be from the past decade. This chapter will concentrate on ions studied by MS and cannot be comprehensive since the literature is too extensive. The literature involving coordination chemistry of gas-phase ions is very extensive and in many cases the quoted sources were often not aware of, or did not consider, the processes being observed as coordination chemistry. This chapter will concentrate on the reactions of transition metal systems and changes in coordination behavior. There will inevitably be similarities of gas- and condensed-phase behavior, but these instances may only be occasionally highlighted. 

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