Barnes

The material of interest is dissolved in a volatile solvent, spread on the surface and allowed to evaporate. As the sweep moves across, compressing the surface, the pressure is measured providing t versus the area per molecule, a. Care must be taken to ensure complete evaporation [1] and the film structure may depend on the nature of the spreading solvent [78]. When the trough area is used to calculate a, one must account for the area due to the meniscus [79]. Barnes and Sharp [80] have introduced a remotely operated barrier drive mechanism for cleaning the water surface while maintaining a closed environment. 

A plot of G x versus composition is shown in Fig. IV-22 for condensed films of octadecanol with docosyl sulfate. Gaines [241] and Cadenhead and Demchak [242] have extended the above approach, and the subject has been extended and reviewed by Barnes and co-workers (see Ref. 243). 

Barnes cautions about using the appropriate units (molecular area with mole fraction, or area per unit mass with mass fraction) when analyzing area data [244]. 

In actual practice the soluble component usually is injected into the substrate solution after the insoluble monolayer has been spread. The reason is that if one starts with the solution, the surface tension may be low enough that the monolayer will not spread easily. McGregor and Barnes have described a useful injection technique [265]. 

Two alternative means around the difficulty have been used. One, due to Pethica [267] (but see also Alexander and Barnes [268]), is as follows. The Gibbs equation, Eq. III-80, for a three-component system at constant temperature and locating the dividing surface so that Fi is zero becomes... 

Fig. IV 23. Penetration of cholesterol monolayers by CTAB (hexadecyl-trimethylam-monium bromide. [From D. M. Alexander, G. T. Barnes, M. A. McGregor, and K. Walker, Phenomena in Mixed Surfactant Systems, in J. F. Scamehom, ed., ACS Symposium Series 311, p. 133, 1986 (Ref. 269). Copyright 1986, American Chemical Society.]...

An interesting consequence of covering a surface with a film is that the rate of evaporation of the substrate is reduced. Most of these studies have been carried out with films spread on aqueous substrates in such cases the activity of the water is practically unaffected because of the low solubility of the film material, and it is only the rate of evaporation and not the equilibrium vapor pressure that is affected. Barnes [273] has reviewed the general subject. 

Barnes and co-workers have studied mixed-monolayer systems [278,281,283,284] and found some striking nonidealities. Mixed films of octadecanol and cholesterol, for example, show little evaporation resistance if only 10% cholesterol is present [278] apparently due to an uneven granular microstructure in films with cholesterol [284]. Another study of cellulose decanoate films showed no correlation between holes in the monolayer and permeation rate [285]. Polymerized surfactants make relatively poor water evaporation retarders when compared to octadecanol [286]. There are problems in obtaining reproducible values for r [287] due to impurities in the monolayer material or in the spreading solvent. 

Barnes and Hunter [290] have measured the evaporation resistance across octadecanol monolayers as a function of temperature to test the appropriateness of several models. The experimental results agreed with three theories the energy barrier theory, the density fluctuation theory, and the accessible area theory. A plot of the resistance times the square root of the temperature against the area per molecule should collapse the data for all temperatures and pressures as shown in Fig. IV-25. A similar temperature study on octadecylurea monolayers showed agreement with only the accessible area model [291]. 

Barnes R J, Dutton G and Sinha A 1997 Unimolecular dissociation of HOCI near threshold quantum state and time-resolved studies J. Phys. Cham. A 101 8374-7... 

Attard G and Barnes C 1998 Surfaces (Oxford Oxford University Press)... 

Kung C, Barnes M D, Lermer N, Whitten W B and Ramsey J M 1999 Single-molecule analysis of ultradilute solutions with guided streams of 1 j.m water droplets Appl. Opt. 38 1481-7... 

Josh Barnes and Piet Hut. A hierarchical o(n log n) force-calculation algorithm. Nature (London), 324 446-449, December 1986. 

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