Condensed monolayer

Two experimental observations led to the conclusion that these lipids were phase-separated in the monolayer condensed state. First, the mean molecular area (Am) varied linearly with the mole fraction of DSPE in the monolayer. Moreover, the data were fit well with a straight line which connected the Am values for the individual lipids, indicative of ideal behavior [34]. These data show that the lipids were either completely phase separated or ideally mixed. The... 

Exposure of thick layers of TDF (on the order of several monolayers) condensed on either Ag(poly) or Li/Ag(poly) at 135 K to the (AES) electron beam for as little as 1 min led to development of a dark spot at the beam position clearly visible with the naked eye. No significant amounts of carbon could be found with AES anywhere on the specimen upon raising the temperature above 300 K, except in the area originally probed by the beam at 135 K. This indicates that the layer of TDF is irreversibly damaged by the electron beam (at least for the current... 

The structural characteristics of the monolayer also depend on the aqueous phase composition. The results suggest that there was an increase in the lipid-subphase interactions when ethanol was added to the aqueous phase. Ethanol molecules tend to be located at the interface between lipid molecules. Thus (i) van der Waals interactions are possible, which explain the monolayer condensation observed from the isotherms and (ii) in addition, dipole-dipole interaction with the polar group produces mono-layer instability by dissolution into the bulk phase. 

The interaction between an acidic phospholipid, the natural (wheat) phosphatidylinositolmonophosphate PI and a linear cationic polysoap the poly(2-methyl-5-vinyl-hexylpyridinium bromide) PVPC6 has been studied with mixed spread monolayers and with hydrated (40%, w/w) mixed bilayers. The "electrostatic" interaction between PI and PVPC6 involves monolayer condensation and affects the bilayers hydration. In addition, the free energy of the bilayers structural water is modulated by this interaction. 

The finite widdi of the adsorption steps of Kr contrasts with what is ohserved on planar graphite, in which a neat adsorption vertical riser is prraent [e.g. 7]. Also, as obsaved by other authors [8], the pressure St which the krypton monolayer condensation occurs is higher on carbon nanotub than on gri hite. This shift originates in the positive curvature of the adsorbent surface, which delays adsorption. Since the condensation of krypton on thick nanotubes should occur at a lower pressure than on thin nanotubes, the pol spersity of the samples can broadem the adsorption stq). The width of the adsorption stqr of Kr on nanotubes could therefore be related the width of the diameter distribution of the tubes. 

Krypton adsorption can be used to qualitatively assess the purity of multi-walled carbon nanotubes samples. The exploited phenomenon is the krypton monolayer condensation that occurs exclusively on the crystalline surface of the nanotubes but not on the catalyst residue, nor on amorphous carbon. In principle, the same methodology could be used with the... 

It seems that below 1.5 statistical monolayers of the surface coverage an adsorbed n-hexane film exists, and above two of these monolayers condensation effects predominate. 

The physical chemist is very interested in kinetics—in the mechanisms of chemical reactions, the rates of adsorption, dissolution or evaporation, and generally, in time as a variable. As may be imagined, there is a wide spectrum of rate phenomena and in the sophistication achieved in dealing wifli them. In some cases changes in area or in amounts of phases are involved, as in rates of evaporation, condensation, dissolution, precipitation, flocculation, and adsorption and desorption. In other cases surface composition is changing as with reaction in monolayers. The field of catalysis is focused largely on the study of surface reaction mechanisms. Thus, throughout this book, the kinetic aspects of interfacial phenomena are discussed in concert with the associated thermodynamic properties. 

There has been much activity in the study of monolayer phases via the new optical, microscopic, and diffraction techniques described in the previous section. These experimental methods have elucidated the unit cell structure, bond orientational order and tilt in monolayer phases. Many of the condensed phases have been classified as mesophases having long-range correlational order and short-range translational order. A useful analogy between monolayer mesophases and die smectic mesophases in bulk liquid crystals aids in their characterization (see [182]). 

The three general states of monolayers are illustrated in the pressure-area isotherm in Fig. IV-16. A low-pressure gas phase, G, condenses to a liquid phase termed the /i uid-expanded (LE or L ) phase by Adam [183] and Harkins [9]. One or more of several more dense, liquid-condensed phase (LC) exist at higher pressures and lower temperatures. A solid phase (S) exists at high pressures and densities. We briefly describe these phases and their characteristic features and transitions several useful articles provide a more detailed description [184-187]. 

Fig. IV-17. A schematic phase diagram illustrating the condensed mesophases found in monolayers of fatty acids and lipids.

As mentioned in Section IX-2A, binary systems are more complicated since the composition of the nuclei differ from that of the bulk. In the case of sulfuric acid and water vapor mixtures only some 10 ° molecules of sulfuric acid are needed for water oplet nucleation that may occur at less than 100% relative humidity [38]. A rather different effect is that of passivation of water nuclei by long-chain alcohols [66] (which would inhibit condensation note Section IV-6). A recent theoretical treatment by Bar-Ziv and Safran [67] of the effect of surface active monolayers, such as alcohols, on surface nucleation of ice shows the link between the inhibition of subcooling (enhanced nucleation) and the strength of the interaction between the monolayer and water. 

There is always some degree of adsorption of a gas or vapor at the solid-gas interface for vapors at pressures approaching the saturation pressure, the amount of adsorption can be quite large and may approach or exceed the point of monolayer formation. This type of adsorption, that of vapors near their saturation pressure, is called physical adsorption-, the forces responsible for it are similar in nature to those acting in condensation processes in general and may be somewhat loosely termed van der Waals forces, discussed in Chapter VII. The very large volume of literature associated with this subject is covered in some detail in Chapter XVII. 

It is evident that boundary lubrication is considerably dependent on the state of the monolayer. Frewing [48] found that, on heating, the value of fi rose sharply near the melting point sometimes accompanied by a change from smooth to stick-slip sliding. Very likely these points of change correspond to the transition between an expanded film and a condensed film in analogy with... 

It is known that even condensed films must have surface diffusional mobility Rideal and Tadayon [64] found that stearic acid films transferred from one surface to another by a process that seemed to involve surface diffusion to the occasional points of contact between the solids. Such transfer, of course, is observed in actual friction experiments in that an uncoated rider quickly acquires a layer of boundary lubricant from the surface over which it is passed [46]. However, there is little quantitative information available about actual surface diffusion coefficients. One value that may be relevant is that of Ross and Good [65] for butane on Spheron 6, which, for a monolayer, was about 5 x 10 cm /sec. If the average junction is about 10 cm in size, this would also be about the average distance that a film molecule would have to migrate, and the time required would be about 10 sec. This rate of Junctions passing each other corresponds to a sliding speed of 100 cm/sec so that the usual speeds of 0.01 cm/sec should not be too fast for pressurized film formation. See Ref. 62 for a study of another mechanism for surface mobility, that of evaporative hopping. 

If an ionic surfactant is present, the potentials should vary as shown in Fig. XIV-5c, or similarly to the case with nonsurfactant electrolytes. In addition, however, surfactant adsorption decreases the interfacial tension and thus contributes to the stability of the emulsion. As discussed in connection with charged monolayers (see Section XV-6), the mutual repulsion of the charged polar groups tends to make such films expanded and hence of relatively low rr value. Added electrolyte reduces such repulsion by increasing the counterion concentration the film becomes more condensed and its film pressure increases. It thus is possible to explain qualitatively the role of added electrolyte in reducing the interfacial tension and thereby stabilizing emulsions. 

The effect is more than just a matter of pH. As shown in Fig. XV-14, phospholipid monolayers can be expanded at low pH values by the presence of phosphotungstate ions [123], which disrupt the stmctival order in the lipid film [124]. Uranyl ions, by contrast, contract the low-pH expanded phase presumably because of a type of counterion condensation [123]. These effects caution against using these ions as stains in electron microscopy. Clearly the nature of the counterion is very important. It is dramatically so with fatty acids that form an insoluble salt with the ion here quite low concentrations (10 M) of divalent ions lead to the formation of the metal salt unless the pH is quite low. Such films are much more condensed than the fatty-acid monolayers themselves [125-127]. 

Fig. XVll-19. Adsorption of CH4 on MgO(lOO) at 77.35 K. The vertical line locates each vertical step corresponds to the condensation of a monolayer. There was no hysteresis. Desorption points are shown as . (From Ref. 110.)...

In the higher pressure sub-region, which may be extended to relative pressure up to 01 to 0-2, the enhancement of the interaction energy and of the enthalpy of adsorption is relatively small, and the increased adsorption is now the result of a cooperative effect. The nature of this secondary process may be appreciated from the simplified model of a slit in Fig. 4.33. Once a monolayer has been formed on the walls, then if molecules (1) and (2) happen to condense opposite one another, the probability that (3) will condense is increased. The increased residence time of (1), (2) and (3) will promote the condensation of (4) and of still further molecules. Because of the cooperative nature of the mechanism, the separate stages occur in such rapid succession that in effect they constitute a single process. The model is necessarily very crude and the details for any particular pore will depend on the pore geometry. 

The first stage in the interpretation of a physisorption isotherm is to identify the isotherm type and hence the nature of the adsorption process(es) monolayer-multilayer adsorption, capillary condensation or micropore filling. If the isotherm exhibits low-pressure hysteresis (i.e. at p/p° < 0 4, with nitrogen at 77 K) the technique should be checked to establish the degree of accuracy and reproducibility of the measurements. In certain cases it is possible to relate the hysteresis loop to the morphology of the adsorbent (e.g. a Type B loop can be associated with slit-shaped pores or platey particles). 

The adsorbed layer at G—L or S—L surfaces ia practical surfactant systems may have a complex composition. The adsorbed molecules or ions may be close-packed forming almost a condensed film with solvent molecules virtually excluded from the surface, or widely spaced and behave somewhat like a two-dimensional gas. The adsorbed film may be multilayer rather than monolayer. Counterions are sometimes present with the surfactant ia the adsorbed layer. Mixed moaolayers are known that iavolve molecular complexes, eg, oae-to-oae complexes of fatty alcohol sulfates with fatty alcohols (10), as well as complexes betweea fatty acids and fatty acid soaps (11). Competitive or preferential adsorption between multiple solutes at G—L and L—L iaterfaces is an important effect ia foaming, foam stabiLizatioa, and defoaming (see Defoamers). 

It was estabhshed ia 1945 that monolayers of saturated fatty acids have quite compHcated phase diagrams (13). However, the observation of the different phases has become possible only much more recendy owiag to improvements ia experimental optical techniques such as duorescence, polarized duorescence, and Brewster angle microscopies, and x-ray methods usiag synchrotron radiation, etc. Thus, it has become well accepted that Hpid monolayer stmctures are not merely soHd, Hquid expanded, Hquid condensed, etc, but that a faidy large number of phases and mesophases exist, as a variety of phase transitions between them (14,15). 

The water removal mechanism is adsorption, which is the mechanism for ad Class 4 drying agents. The capacity of such materials is often shown in the form of adsorption isotherms as depicted in Figures 9a and 9b. The initial adsorption mechanism at low concentrations of water is beheved to occur by monolayer coverage of water on the adsorption sites. As more water is adsorbed, successive layers are added until condensation or capidary action takes place at water saturation levels greater than about 70% relative humidity. At saturation, ad the pores are fided and the total amount of water adsorbed, expressed as a Hquid, represents the pore volume of the adsorbent. 

At a distance of 20 cm from the orifice a plate of 1 cm diameter receives 1.67 X 10 particles/second. If all these particles are condensed, and each has a diameter of 0.2 nm, the time to form a monolayer of condensate is 1.5 seconds. 

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