Water-rich system

Below some critical surfactant concentration, the system is two-phase with excess oil or water depending on the oil/water concentration. On adding more surfactant, the system moves into a one-phase region with normal micelles forming in water-rich systems. The water constitutes the continuous phase, solvating the headgroups of the surfactant whose hydro-phobic tails solubilise oil in the core of the micelle. In oil rich systems, reverse-micelles form. With further increases in surfactant composition. 

Hydrotropes with their gel-prevention action are an essential part of liquid cleaners for which they provide two essential functions (a) they allow high surfactant concentrations in the formulation by preventing its gelling at the low water concentrations employed, and (b) they prevent gel formation in extremely water-rich systems under laundering conditions. 

The results are straight forward and the interpretation immediately evident. The liquid crystalline phase formed in these extremely water rich systems was destabilized by the dicarboxylic acid and transformed to an isotropic solution. The conclusion that the hydrotropic action of the dicarboxylic acid is intimately related to its capacity to destabilize a liquid crystalline phase also under the water-rich conditions during actual laundering conditions appears well justified. 

The above rules of thumb apply to organic and hydrocarbon systems, whose surface tensions are relatively low (a < 25 mN/m). For higher surface tensions, the liquid does not adhere well to the packing surfaces (underwetting), causing higher HETPs. In a water-rich system (a = 70 mN/m or so) HETPs obtained from Eqs. (14-156), (14-158), and (14-159) need to be doubled. For intermediate surface tension systems (some amines and glycols, whose surface tension at column conditions is 40 to 50 mN/m), HETPs obtained from Eqs. (14-156), (14-158), and (14-159) need to be multiplied by 1.5. 

Physical properties. Data presented by a number of workers (98,115,119,120) suggest that generally, random packing HETP is relatively insensitive to system properties. A survey of the data in Chap. 11 will lead to a similar conclusion. The data in Chap. 11 also indicate that the insensitivity to system physical properties extends to nonaqueous systems in structured packings. For water-rich systems, structured-packing HETPs tend to be much higher than for nonaqueous systems (Sec. 8.1.10). 

In the case of water rich systems, the connectivity of the system cannot be evidenced in a so-direct way. Nevertheless, forced Rayleigh scattering and fluorescence photo-bleaching experiments are currently under way to elucidate this point (with L. Leger, College de France). 

In this case of water rich systems, there is no evident model of interaction and Van der Waals forces between droplets are too weak to lead to a critical point which seems to be of 01 quite different kind from the one near S2. The phase diagram of the system is possibly too complicated to study this particular point but it seems that the critical point near S is a lower critical point. In that case, one may think that entropic forces are important in the medium. In order to confirm this point, we have studied simpler systems oil free systems. 

In the case of the water-rich systems, the approach to the critical point seems to be quite different. Ultrasonic adsorption experiments show no evidence of surfactant exchange even close to the boundary Sj(18). We rather observe an elongation of the droplets. In those systems, entropic forces must be dominant as evidenced by the study of a simpler system. 

The basic mode of mesophase formation is as described above for CTAB. However, as one might expect, things are not quite so straightforward and there are various types of mesophase which can be formed from various types of surfactant. The surfactant structure can be varied so that fluorocarbon chains can be employed in place of the hydrocarbon variety, while anionic (e. g. -SOa") and the neutral (e.g. -(0CH2CH2) -0H) polar headgroups are often used. These surfactants can then form a variety of different mesophases as a function of (mainly) concentration in the solvent of choice (normally water). These phases are the lamellar (L ) phase, a simple bilayer phase, and variations on the cubic (li, I2, Vi, V2) and hexagonal (H, H2) phases. For these last phases, the subscript 1 implied a normal phase as found in a water-rich system, while the subscript 2 implied a reversed phase as found in an oil-rich system. For the cubic phases, the letter F implied a micellar phase (e. g. 

The colloidal properties of anionically prepared poly(styrene-g-ethylene oxide) graft copolymers were studied by Candau et al. in different water/toluene/ alcohol mixtures by light and neutron scattering, NMR, and viscometry [307-309]. Aggregation numbers depend on mixture compositions with the highest values attained for water-rich systems. The micelles formed seem to have a core and shell conformation, with PS cores, in all cases studied. Dialysis experiments showed that the enhanced water-oil solubility was due to preferential solvation of the two segregated components of the copolymers by the solvent mixture and not to one specific solvent entrapment as is the case of classical microemulsions. 

Efficiency. It has been shown that an increase of the microemulsion pentanol content can increase the efficiency [5], Conversely, a drastic decrease of efficiency has been observed upon increasing the heptane content m the microemulsion [5]. The toluene efficiency dropped from 7000 plates with Microemulsion 1 (without heptane) to 3300 plates with Microemulsion 3 (heptane 0.59% w/w). The decylbenzene peak efficiency was divided by 8 with the same addition of heptane (1150 plates and 140 plates, respectively) [5], It was speculated that the significant decrease in the kmetics of the solute exchange between the stationary phase and the microemulsion droplets was linked to physicochemical structural changes of the system [5]. The large solubility power of o/w microemulsion systems, up to 4 g/L of decylbenzene in a 90% water rich system, produced a unique selectivity. Unfortunately the low-efficiency problem hinders the use of such systems. 

In the third system studied, OA in 1-monocaproin solution, none or moderate interaction is supposed to occur, since it has been shown [12,13] that non-ionic amphiphiles only possess weak affinity, if any, to water-soluble proteins. 1-Monocaproin has interesting phase behaviour in aqueous systems. Only one liquid phase exists [14] in water-rich systems ordinary micelles are formed and in amphiphile-rich systems the isotropic liquid phase is of the L2 type. The interfacial behaviour of this component has not yet been reported. 

Many pairs of partially miscible liquids possess neither a lower nor an upper C.S.T. for reasons outlined in the previous paragraph. Thus consider the two liquid phases from the two components water and diethyl ether. Upon cooling the system at constant pressure, a point will be reached when a third phase, ice, will form, thus rendering the production of a lower C.S.T. impossible, likewise, if the temperature of the two layers is raised, the critical point for the ether rich layer will be reached while the two liquid phases have different compositions. Above the critical point the ether-rich layer will be converted into vapour, and hence the system will be convert into a water rich liquid and an ether rich vapour the upper C.S.T. cannot therefore be attained. 

The accompanying sketch qualitatively describes the phase diagram for the system nylon-6,6, water, phenol for T > 70°C.f In this figure the broken lines are the lines whose terminals indicate the concentrations of the three components in the two equilibrium phases. Consult a physical chemistry textbook for the information as to how such concentrations are read. In the two-phase region, both phases contain nylon, but the water-rich phase contains the nylon at a lower concentration. On this phase diagram or a facsimile, draw arrows which trace the following procedure ... 

Based on Hquid—Hquid equiHbrium principles, a general model of octanol—water partitioning is possible if accurate activity coefficients can be determined. First, phase equiHbrium relationships based on activity coefficients permit Hquid—Hquid equiHbrium calculations for the biaary octanol—water system. Because the two components are almost immiscible ia each other, two phases form an octanol-rich phase containing dissolved water, and a water-rich phase containing dissolved octanol. 

Strkcttire inflkence. The specificity of interphase transfer in the micellar-extraction systems is the independent and cooperative influence of the substrate molecular structure - the first-order molecular connectivity indexes) and hydrophobicity (log P - the distribution coefficient value in the water-octanole system) on its distribution between the water and the surfactant-rich phases. The possibility of substrates distribution and their D-values prediction in the cloud point extraction systems using regressions, which consider the log P and values was shown. Here the specificity of the micellar extraction is determined by the appearance of the host-guest phenomenon at molecular level and the high level of stmctural organization of the micellar phase itself. 

On the basis of data obtained the possibility of substrates distribution and their D-values prediction using the regressions which consider the hydrophobicity and stmcture of amines was investigated. The hydrophobicity of amines was estimated by the distribution coefficient value in the water-octanole system (Ig P). The molecular structure of aromatic amines was characterized by the first-order molecular connectivity indexes ( x)- H was shown the independent and cooperative influence of the Ig P and parameters of amines on their distribution. Evidently, this fact demonstrates the host-guest phenomenon which is inherent to the organized media. The obtained in the research data were used for optimization of the conditions of micellar-extraction preconcentrating of metal ions with amines into the NS-rich phase with the following determination by atomic-absorption method. 

Lattice models for bulk mixtures have mostly been designed to describe features which are characteristic of systems with low amphiphile content. In particular, models for ternary oil/water/amphiphile systems are challenged to reproduce the reduction of the interfacial tension between water and oil in the presence of amphiphiles, and the existence of a structured disordered phase (a microemulsion) which coexists with an oil-rich and a water-rich phase. We recall that a structured phase is one in which correlation functions show oscillating behavior. Ordered lamellar phases have also been studied, but they are much more influenced by lattice artefacts here than in the case of the chain models. 

FIG. 13 Phase diagram of a vector lattice model for a balanced ternary amphiphilic system in the temperature vs surfactant concentration plane. W -I- O denotes a region of coexistence between oil- and water-rich phases, D a disordered phase, Lj an ordered phase which consists of alternating oil, amphiphile, water, and again amphi-phile sheets, and L/r an incommensurate lamellar phase (not present in mean field calculations). The data points are based on simulations at various system sizes on an fee lattice. (From Matsen and Sullivan [182]. Copyright 1994 APS.)... 

The function /[0(r)] has three minima by construction and guarantees three-phase coexistence of the oil-rich phase, water-rich phase, and microemulsion. The minima for oil-rich and water-rich phases are of equal depth, which makes the system symmetric, therefore fi is zero. Varying the parameter /o makes the microemulsion more or less stable with respect to the other two bulk uniform phases. Thus /o is related to the chemical potential of the surfactant. The constant g2 depends on go /o and is chosen in such a way that the correlation function G r) = (0(r)0(O)) decays monotonically in the oil-rich and water-rich phases [12,13]. This is the case when gi > 4y/l +/o - go- Here we take, arbitrarily, gj = 4y l +/o - go + 0.01. 

An example for a partially known ternary phase diagram is the sodium octane 1 -sulfonate/ 1-decanol/water system [61]. Figure 34 shows the isotropic areas L, and L2 for the water-rich surfactant phase with solubilized alcohol and for the solvent-rich surfactant phase with solubilized water, respectively. Furthermore, the lamellar neat phase D and the anisotropic hexagonal middle phase E are indicated (for systematics, cf. Ref. 62). For the quaternary sodium octane 1-sulfonate (A)/l-butanol (B)/n-tetradecane (0)/water (W) system, the tricritical point which characterizes the transition of three coexisting phases into one liquid phase is at 40.1°C A, 0.042 (mass parts) B, 0.958 (A + B = 56 wt %) O, 0.54 W, 0.46 [63]. For both the binary phase equilibrium dodecane... 

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