Surfactants insoluble monolayers

The question may then be raised as to whether insoluble monolayers may really be treated in terms of equilibrium thermodynamics. In general, this problem has been approached by considering (i) the equilibrium spreading pressure of the monolayer in the presence of the bulk crystalline surfactant, and (ii) the stability of the monolayer film as spread from solution. These quantities are obtained experimentally and are necessary in any consideration of film thermodynamic properties. In both cases, time is clearly a practical variable. 

The difference between the static or equilibrium and dynamic surface tension is often observed in the compression/expansion hysteresis present in most monolayer Yl/A isotherms (Fig. 8). In such cases, the compression isotherm is not coincident with the expansion one. For an insoluble monolayer, hysteresis may result from very rapid compression, collapse of the film to a surfactant bulk phase during compression, or compression of the film through a first or second order monolayer phase transition. In addition, any combination of these effects may be responsible for the observed hysteresis. Perhaps understandably, there has been no firm quantitative model for time-dependent relaxation effects in monolayers. However, if the basic monolayer properties such as ESP, stability limit, and composition are known, a qualitative description of the dynamic surface tension, or hysteresis, may be obtained. 

Finally, surfactants have also been used to reduce water evaporation from open reservoirs in arid areas, especially in Australia. The packed insoluble monolayer adsorbed at the air/water interface substantially reduces the transfer of water vapour to the atmosphere. Cetylalcohol is used at the rate of 1 ounce per acre per day for this reason. It has been calculated that this procedure can save up to one million gallons per acre per year. 

In the case of adsorption from solution, the surfactant layers are in equilibrium with the solution and will de-sorb on dilution. However, it would be very useful to produce adsorbed layers in both air and water, which will remain adsorbed. This can be achieved using the Langmuir-Blodgett deposition technique. The technique is based on the observation that if a surfactant, which is insoluble in water, is dissolved in a volatile, non-aqueous solvent and then spread on water, an insoluble monolayer of orientated surfactant molecules will remain at the air/solution interface. The effect of the spreading surfactant and its surface film pressure can be dramatically demonstrated by spreading hydrophobic talc powder on a clean water surface and then placing a... 

When a surfactant is injected into the liquid beneath an insoluble monolayer, surfactant molecules may adsorb at the surface, penetrating between the monolayer molecules. However it is difficult to determine the extent of this penetration. In principle, equilibrium penetration is described by the Gibbs equation, but the practical application of this equation is complicated by the need to evaluate the dependence of the activity of monolayer substance on surface pressure. There have been several approaches to this problem. In this paper, previously published surface pressure-area Isotherms for cholesterol monolayers on solutions of hexadecy1-trimethyl-ammonium bromide have been analysed by three different methods and the results compared. For this system there is no significant difference between the adsorption calculated by the equation of Pethica and that from the procedure of Alexander and Barnes, but analysis by the method of Motomura, et al. gives results which differ considerably. These differences indicate that an independent experimental measurement of the adsorption should be capable of discriminating between the Motomura method and the other two. 

Monolayers are best formed from water-insoluble molecules. This is expressed well by the title of Gaines s classic book Insoluble Monolayers at Liquid-Gas Interfaces [104]. Carboxylic acids (7-13 in Table 1, for example), sulfates, quaternary ammonium salts, alcohols, amides, and nitriles with carbon chains of 12 or longer meet this requirement well. Similarly, well-behaved monolayers have been formed from naturally occurring phospholipids (14-17 in Table 1, for example), as well as from their synthetic analogs (18,19 in Table 1, for example). More recently, polymerizable surfactants (1-4, 20, 21 in Table 1, for example) [55, 68, 72, 121], preformed polymers [68, 70, 72,122-127], liquid crystalline polymers [128], buckyballs [129, 130], gramicidin [131], and even silica beads [132] have been demonstrated to undergo monolayer formation on aqueous solutions. 

Composition of the subphase is of paramount importance for monolayer formation. Electrolytes, by virtue of their ability to salt-out organic molecules, often render surfactants insoluble and, thus, permit the formation of a well-behaved monolayer. A case in point is the previously cited example of optically active (jV-(a-methylbenzyl)stearamides [114]. Stable monolayers could not be formed with these molecules on water. Stable monolayers readily formed, however, on strong aqueous acid solutions [114],... 

INSOLUBLE MONOLAYERS SPREADING OF SURFACTANTS ON AQUEOUS SURFACES... 

E. Ruckenstein Phase transitions in insoluble monolayers of surfactants, Encyclopedia of Surface and Colloid Science (2007) Taylor Francis. 

Ruckenstein, E. Nonconventional first order transitions in insoluble monolayers of surfactants. Colloids and Surfaces A 2001,183, 423. 

Ruckenstein," E. Li, B. A surface equation of state based on clustering of surfactant molecules of insoluble monolayers. Langmuir 1995,11, 3510. 

Black spot formation discussed here was carried out with foam films from soluble surfactants. The formation of foam films, especially of black films, from insoluble monolayers is also interesting. This will be considered in the next Section. 

Data on emulsion film formation from insoluble surfactant monolayer are rather poor. It is known, however, that such films can be obtained when a bubble is blown at the surface of insoluble monolayers on an aqueous substrate [391,392]. Richter, Platikanov and Kretzschmar [393] have developed a technique for formation of black foam films which involves blowing a bubble at the interface of controlled monolayer (see Chapter 2). Experiments performed with monolayers from DL-Py-dipalmitoyl-lecithin on 510 3 mol dm 3 NaCl aqueous solution at 22°C gave two important results. Firstly, it was established that foam films, including black films, with a sufficiently long lifetime, formed only when the monolayer of lecithin molecules had penetrated into the bubble surface as well, i.e. there are monolayers at both film surfaces on the contrary a monolayer, however dense, formed only at one of the film surfaces could not stabilize it alone and the film ruptured at the instant of its formation. Secondly, relatively stable black films formed at rather high surface pressures of the monolayer at area less than 53A2 per molecule, i.e. the monolayer should be close-packed, which corresponds to the situation in black films stabilized with soluble surfactants. 

In section 6.2.4 we examined the case in which the surface of a solution containing an amphiphile became covered with a monomol-ecular film as a result of spontaneous adsorption from solution. The molecules in such films are in equilibrium with those in the bulk of the solution, i.e. there is a continuous movement of molecules between the surface and the solution below it. If, however, a surfactant has a very long hydrocarbon chain it will be insufficiently water-soluble for a film to be formed in this way. In such cases we can spread a film on the surface of the solution by dissolving the surfactant in a suitable volatile solvent and carefully injecting the solution on to the surface. The insoluble monolayer formed by this process contains all of the molecules injected on the surface there is no equilibrium with the bulk solution because of the low water solubility of the surfactant. Conse-... 

Frysinger GS, Asher WE, Korenowski GM, Barger WR, Klusty MA, Frew NM and Nelson RK (1992) Studies of ocean slicks by nonlinear laser processes, Part 1 Second-harmonic generation. J Geophys Res 97 5253-69 Hirsa, A, Korenowski, G. M., Logory, L. M. Judd, C. D. (1997) Determination of surface viscosities by surfactant concentration and velocity measurements for an insoluble monolayer . Langmuir, 13, 3813-3822. 

Figure 5.3 Film balances a. Langmuir trough having a movable barrier and a Wilhelmy tensiometer to measure the spreading pressure, n, for water insoluble monolayers, b. PLAWM (Pockels, Langmuir, Adam, Wilson and McBain) trough used for partially water-soluble monolayers, where a flexible membrane, which is fixed to the barrier, separates the surfactant solution and pure water departments to prevent the passage of dissolved surfactant molecules into the pure water department beneath the barrier.

Fig. 11. Stable, insoluble monolayers from polymerized surfactants of head geometry, a = 29, b = 30, c = 31, d = 32 data from [232,245]...

---