Langmuir interfaces

Using Langmuir s principle of independent surface action, make qualitative calculations and decide whether the polar or the nonpolar end of ethanol should be oriented toward the mercury phase at the ethanol-mercury interface. 

A belief that solid interfaces are easier to understand than liquid ones shifted emphasis to the former but the subjects are not really separable, and the advances in the one are giving impetus to the other. There is increasing interest in films of biological and of liquid crystalline materials because of the importance of thin films in microcircuitry (computer chips ), there has been in recent years a surge of activity in the study of deposited mono- and multilayers. These Langmuir-Blodgett films are discussed in Section XV-7. 

Interferometry is based on the fact that light reflected from the front and back interfaces of a film travels different distances, producing interference effects. The method has been applied to Langmuir-Blodgett films (Section XV-7) and to soap films (Section XrV-8) [147-149]. 

The external reflection of infrared radiation can be used to characterize the thickness and orientation of adsorbates on metal surfaces. Buontempo and Rice [153-155] have recently extended this technique to molecules at dielectric surfaces, including Langmuir monolayers at the air-water interface. Analysis of the dichroic ratio, the ratio of reflectivity parallel to the plane of incidence (p-polarization) to that perpendicular to it (.r-polarization) allows evaluation of the molecular orientation in terms of a tilt angle and rotation around the backbone [153]. An example of the p-polarized reflection spectrum for stearyl alcohol is shown in Fig. IV-13. Unfortunately, quantitative analysis of the experimental measurements of the antisymmetric CH2 stretch for heneicosanol [153,155] stearly alcohol [154] and tetracosanoic [156] monolayers is made difflcult by the scatter in the IR peak heights. 

Assume that an aqueous solute adsorbs at the mercury-water interface according to the Langmuir equation x/xm = bc/( + be), where Xm is the maximum possible amount and x/x = 0.5 at C = 0.3Af. Neglecting activity coefficient effects, estimate the value of the mercury-solution interfacial tension when C is Q.IM. The limiting molecular area of the solute is 20 A per molecule. The temperature is 25°C. 

Assume that a salt, MX (1 1 type), adsorbs at the mercury-water interface according to the Langmuir equation ... 

The usual situation, true for the first three cases, is that in which the reactant and product solids are mutually insoluble. Langmuir [146] pointed out that such reactions undoubtedly occur at the linear interface between the two solid phases. The rate of reaction will thus be small when either solid phase is practically absent. Moreover, since both forward and reverse rates will depend on the amount of this common solid-solid interface, its extent cancels out at equilibrium, in harmony with the thermodynamic conclusion that for the reactions such as Eqs. VII-24 to VII-27 the equilibrium constant is given simply by the gas pressure and does not involve the amounts of the two solid phases. 

Films spread at liquid-liquid interfaces or on liquids other than water are discussed followed by the important effects of charged monolayers on water. Finally, the most technologically important application of Langmuir films, the Langmuir-Blodgett film deposited on a solid substrate, is reviewed. 

Holmberg M ef al 1997 Surface force studies of Langmuir-Blodgett cellulose films J. Colloid Interface Sci. 186 369-81... 

Nierengarten J-F, Schall C, Nicoud J-F, Fleinrich B and Guillen D 1998 Amphiphilic cyclic fullerene bisadducts synthesis and Langmuir films at the air-water interface Tetrahedron Lett. 39 5747-50... 

Peterson I R, Veale G and Montgomery C M 1986 The preparation of oleophilio surfaoes for Langmuir-Blodgett deposition J. Colloid Interface Sc/. 109 527-30... 

Tieke B and Weiss K 1984 The morphology of Langmuir-Blodgett multilayers of amphiphilio diaoetylenes—effeots of the preparation oonditions and the role of additives J. Colloid Interface Sol. 101 129-48... 

McFadden C F and Geiiman A J 1995 Ultra-high vacuum boundary lubrication of the Cu-Cu interface by 2,2,2-trifluoroethanol Langmuir 273-80... 

Anotlier metliod applicable to interfaces is tlie detennination of tlie partial molecular area (7 of a biopolynier partitioning into a lipid monolayer at tlie water-air interface using tlie Langmuir trough [28]. The first step is to record a series of pressure 71-area (A) isotlienns witli different amounts of an amphiphilic biopolynier spread at tlie interface. 

Langmuir-Blodgett was the first technique to provide a practical route for the constmction of ordered molecular assembhes. These monolayers, which provide design dexibiUty both at the individual molecular and at the material levels, are prepared at the water—air interface using a hiUy computerized trough (Fig. 1). Detailed discussions of troughs (4) and of surface pressure, 7T, and methods of surface pressure measurements are available (3,6). 

Patterns of ordered molecular islands surrounded by disordered molecules are common in Langmuir layers, where even in zero surface pressure molecules self-organize at the air—water interface. The difference between the two systems is that in SAMs of trichlorosilanes the island is comprised of polymerized surfactants, and therefore the mobihty of individual molecules is restricted. This lack of mobihty is probably the principal reason why SAMs of alkyltrichlorosilanes are less ordered than, for example, fatty acids on AgO, or thiols on gold. The coupling of polymerization and surface anchoring is a primary source of the reproducibihty problems. Small differences in water content and in surface Si—OH group concentration may result in a significant difference in monolayer quahty. Alkyl silanes remain, however, ideal materials for surface modification and functionalization apphcations, eg, as adhesion promoters (166—168) and boundary lubricants (169—171). 

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... 

A particularly simple lattice model has been utilized by Harris and Rice [129] and subsequently by Stettin et al. [130] to simulate Langmuir mono-layers at the air/water interface chains on a cubic lattice which are confined to a plane at one end. Haas et al. have used the bond-fluctuation model, a more sophisticated chain model which is common in polymer simulations, to study the same system [131]. Amphiphiles are modeled as short chains of monomers which occupy a cube of eight sites on a cubic lattice and are connected by bonds of variable length [132], At high surface coverage, Haas et al. report various lattice artefacts. They conclude that the study... 

The area of colloids, surfactants, and fluid interfaces is large in scope. It encompasses all fluid-fluid and fluid-solid systems in which interfacial properties play a dominant role in determining the behavior of the overall system. Such systems are often characterized by large surface-to-volume ratios (e.g., thin films, sols, and foams) and by the formation of macroscopic assembhes of molecules (e.g., colloids, micelles, vesicles, and Langmuir-Blodgett films). The peculiar properties of the interfaces in such media give rise to these otherwise unlikely (and often inherently unstable) structures. 

The second way of preparing L-B monolayer structures, the horizontal lifting method, was introduced by Langmuir and Schaefer. In this method, a compressed monolayer first is formed at the water-air interface, and a flat substrate is then placed horizontally on the monolayer film. When the substrate is lifted and separated from the water surface, the monolayer is transferred onto the substrate, as depicted in Fig. 15(d). 

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