Interface liquid phase transition

The physical properties of materials in a confined state have attracted considerable attention both due to their fundamental significance and to their primary importance for nanotechnology. The term confined state embraces a wide variety of systems the boundary layers at the interfaces between two bulk phases, the adsorption layers, wetting films, epitaxial structures, emulsions, free-lying nanoparticles and particles embedded in solid matrices, the substances condensed in pores, and so on. As a rule, the transition of a substance from the bulk state to the confined state is accompanied by an essential alteration of many physical properties. In particular, for practically all of the confined systems mentioned above, a shift of the first order phase transition temperature with respect to that in the bulk state was detected experimentally (see [1-4] for reviews). In nanoporous systems, not only a considerable (tens of degrees) depression of the freezing temperature can be observed, but the transition to solid state might even disappear. At the same time there are systems that demonstrate not a depression but an elevation of the solid/liquid phase transition temperature in pores. A similar situation occurs with small particles, adsorbed films and boundary layers at plane interfaces. 

Surface SHG [4.307] produces frequency-doubled radiation from a single pulsed laser beam. Intensity, polarization dependence, and rotational anisotropy of the SHG provide information about the surface concentration and orientation of adsorbed molecules and on the symmetry of surface structures. SHG has been successfully used for analysis of adsorption kinetics and ordering effects at surfaces and interfaces, reconstruction of solid surfaces and other surface phase transitions, and potential-induced phenomena at electrode surfaces. For example, orientation measurements were used to probe the intermolecular structure at air-methanol, air-water, and alkane-water interfaces and within mono- and multilayer molecular films. Time-resolved investigations have revealed the orientational dynamics at liquid-liquid, liquid-solid, liquid-air, and air-solid interfaces [4.307]. 

Another interesting class of phase transitions is that of internal transitions within amphiphilic monolayers or bilayers. In particular, monolayers of amphiphiles at the air/water interface (Langmuir monolayers) have been intensively studied in the past as experimentally fairly accessible model systems [16,17]. A schematic phase diagram for long chain fatty acids, alcohols, or lipids is shown in Fig. 4. On increasing the area per molecule, one observes two distinct coexistence regions between fluid phases a transition from a highly diluted, gas -like phase into a more condensed liquid expanded phase, and a second transition into an even denser... 

For systems where the bulk freezing transition is well understood, one may want to go one step further and investigate the modifications of the phase transition and the sohd phases in the event of external influence on the system. Flow does freezing happen in a confined situation where external boundaries are present What is freezing in porous media like A related question is What does the interface between sohd and liquid look like This is an intrinsic inhomogeneity that the system builds up by itself (if, as usual, the transition is first order). Let us describe some papers dealing with freezing under external influence. 

The terminology of L-B films originates from the names of two scientists who invented the technique of film preparation, which transfers the monolayer or multilayers from the water-air interface onto a solid substrate. The key of the L-B technique is to use the amphiphih molecule insoluble in water, with one end hydrophilic and the other hydrophobic. When a drop of a dilute solution containing the amphiphilic molecules is spread on the water-air interface, the hydrophilic end of the amphiphile is preferentially immersed in the water and the hydrophobic end remains in the air. After the evaporation of solvent, the solution leaves a monolayer of amphiphilic molecules in the form of two-dimensional gas due to relatively large spacing between the molecules (see Fig. 15 (a)). At this stage, a barrier moves and compresses the molecules on the water-air interface, and as a result the intermolecular distance decreases and the surface pressure increases. As the compression from the barrier proceeds, two successive phase transitions of the monolayer can be observed. First a transition from the gas" to the liquid state. 

The mobile phase in LC-MS may play several roles active carrier (to be removed prior to MS), transfer medium (for nonvolatile and/or thermally labile analytes from the liquid to the gas state), or essential constituent (analyte ionisation). As LC is often selected for the separation of involatile and thermally labile samples, ionisation methods different from those predominantly used in GC-MS are required. Only a few of the ionisation methods originally developed in MS, notably El and Cl, have found application in LC-MS, whereas other methods have been modified (e.g. FAB, PI) or remained incompatible (e.g. FD). Other ionisation methods (TSP, ESI, APCI, SSI) have even emerged in close relationship to LC-MS interfacing. With these methods, ion formation is achieved within the LC-MS interface, i.e. during the liquid- to gas-phase transition process. LC-MS ionisation processes involve either gas-phase ionisation (El), gas-phase chemical reactions (Cl, APCI) or ion evaporation (TSP, ESP, SSI). Van Baar [519] has reviewed ionisation methods (TSP, APCI, ESI and CF-FAB) in LC-MS. 

The orientation of molecules at the interface depends on an interaction with both the surface and the molecules in the liquid phase, and also on the interaction within the adsorbed layer. The interaction of molecules with the electrode is stronger the weaker their interaction with other molecules in the bulk. The correlation between and 0 is linear but different for the transition metals and the sp metals. Owing to the tendency to form chemisorption bonds, transition metals bind water molecules more strongly than the sp metals. 

The model also predicts that if the interface temperature exceeds the critical temperature of the colder liquid, vapor blanketing should always result and no rapid phase transitions could occur. 

In the Chapter 7, formation of monolayers in air-liquid interfaces and the resulting film pressure and phase transitions are discussed. This chapter also includes a brief discussion of adsorption on solid surfaces from solutions. 

---