Micelle cloud point

Performance Indices Quality Factors Optimum E1LB Critical micelle concentration (CMC) Soil solubilization capacity Krafft point (ionic surfactants only) Cloud point (nonionic surfactants only) Viscosity Calcium binding capacity Surface tension reduction at CMC Dissolution time Material and/or structural attributes... 

Krafft point (for ionic surfactants) and cloud point (for nonionic surfactants) are both a limit to surfactant solubility. The solubility of ionic surfactants decreases significantly below the Krafft point, since its concentration falls below the CMC and individual surfactant molecules cannot form micelles. Therefore, the Krafft point of an ionic surfactant must be below the desired wash temperature for maximum soil removal. In contrast, the solubility of some nonionic surfactants decreases with increasing temperature. Above the cloud point, the surfactant becomes insoluble. Thus, the cloud point of a nonionic surfactant should be 15-30°C above the intended wash temperature [8],... 

The effect characteristic of a multi-chain hydrophobe, that is, increase in the cmc and simultaneous decrease in the cloud point, appears to be inconsistent with the well-known HLB concept in surfactants. Tanford has pointed out that based on geometric considerations of micellar shape and size, amphiphilic molecules having a double-chain hydrophobe tend to form a bilayer micelle more highly packed rather than those of single-chain types ( ). In fact, a higher homologue of a,a -dialkylglyceryl polyoxyethylene monoether has been found to form a stable vesicle or lamellar micelle (9 ). Probably, the multi-chain type nonionics listed in... 

This phenomenon can be exploited for separation and concentration of solutes. If one solute has certain affinity for the micellar entity in solution then, by altering the conditions of the solution to ensure separation of the micellar solution into two phases, it is possible to separate and concentrate the solute in the surfactant-rich phase. This technique is known as cloud point extraction (CPE) or micelle-mediated extraction (ME). The ratio of the concentrations of the solute in the surfactant-rich phase to that in the dilute phase can exceed 500 with phase volume ratios exceeding 20, which indicates the high efficiency of this technique. Moreover, the surfactant-rich phase is compatible with the micellar and aqueous-organic mobile phases in liquid chromatography and thus facilitates the determination of chemical species by different analytical methods [104]. 

Carrying out an emulsion polymerization requires an awareness of the krafft point of an ionic surfactant and the cloud point of a nonionic surfactant. Micelles are formed only at temperatures above the Krafft point of an ionic surfactant. For a nonionic surfactant, micelles are formed only at temperatures below the cloud point. Emulsion polymerization is carried out below the cloud temperature of a nonionic surfactant and above the Krafft temperature of an ionic surfactant. 

The PPO block is temperature-sensitive, with an LCST (cloud point) of around 15 °C, whereas the DEA block is pH-responsive. At pH 6.5 and 5°C, both blocks are solvated and the copolymer is molecularly dissolved in aqueous solution. On adjusting the solution pH to pH 8.5, the DEA block becomes deprotonated and hence hydrophobic, leading to the formation of DEA-core micelles at 5 °C. On the other hand, if the pH is held constant at pH 6.5 and the temperature is raised above the LCST of the PPO block, PPO-core micelles are obtained with the weakly cationic DEA chains forming the micelle coronas. Since these new diblock copolymers can exist in two micellar states we have christened them schizophrenic copolymers. ... 

The effect of using mixtures of surfactants on micelle formation, monolayer formation, solubilization, adsorption, precipitation, and cloud point phenomena is discussed. Mechanisms of surfactant interaction and some models useful in describing these phenomena are outlined. The use of surfactant mixtures to solve technological problems is also considered. 

This overview will outline surfactant mixture properties and behavior in selected phenomena. Because of space limitations, not all of the many physical processes involving surfactant mixtures can be considered here, but some which are important and illustrative will be discussed these are micelle formation, monolayer formation, solubilization, surfactant precipitation, surfactant adsorption on solids, and cloud point Mechanisms of surfactant interaction will be as well as mathematical models which have been be useful in describing these systems,... 

In order to define a ionic/nonionic surfactant solution with high salinity/hardness tolerance, the following criterion should be followed. The mixed micelle should have as large of a negative deviation from ideality as possible. Surfactant mixture characteristics which result in this have already been discussed. The nonionic surfactant should have a high cloud point. Otherwise the amount of nonionic surfactant which can be added to the system is limited to low levels before phase separation occurs. If possible, a mixed ionic surfactant should be used for reasons Just discussed. There is no such benefit to using mixed nonionic surfactants, although this is not necessarily detrimental either. 

The cloud point of a mixture of nonionic surfactants is intermediate between the pure nonionic surfactants involved (95.99) The cloud point of a dilute nonionic surfactant solution increases upon addition of ionic surfactant (95.98—104). The coacervate phase forms because of attractive forces between the micelles in solution. The incorporation of ionic surfactant into the nonionic micelles introduces electrostatic repulsion between micelles, causing coacervate phase formation to be hindered, raising the cloud point. 

The equilibrium in these systems above the cloud point then involves monomer-micelle equilibrium in the dilute phase and monomer in the dilute phase in equilibrium with the coacervate phase. Prediction o-f the distribution of surfactant component between phases involves modeling of both of these equilibrium processes (98). It should be kept in mind that the region under discussion here involves only a small fraction of the total phase space in the nonionic surfactant—water system (105). Other compositions may involve more than two equilibrium phases, liquid crystals, or other structures. As the temperature or surfactant composition or concentration is varied, these regions may be encroached upon, something that the surfactant technologist must be wary of when working with nonionic surfactant systems. 

As the temperature of a mixed surfactant system is increased above its cloud point, the coacervate (concentrated) phase may go from a concentrated micellar solution mixed ionic/nonionic systems, it would be of interest to measure thermodynamic properties of mixing in this coacervate as this temperature increased to see if the changes from micelle to concentrated coacervate were continuous or if discontinuities occurred at certain temperatures/compositions. The similarities and differences between the micelle and coacervate could be made clearer by such an experiment. 

PS-PB-PS = 70.10% M, = 101, 14% Ethyl acetate Formation of worm-like micelles from spherical micelles, associated with cloud point Turbidometry, TEM. SLS Canham et at (1980)... 

Caution should be exercised when considering temperature effects on solubilization by micelles, since the aqueous solubility of the solute and thus its micelle/water partition coefLcient can also change in response to temperature changes. For example, it has been reported that although tt solubility of benzoic acid in a series of polyoxyethylene nonionic surfactants increases with temperature, the micelle/water partition coefLci rt, shows a minimum at 2C, presumably due to the increase in the aqueous solubility of benzoic acid (Humphreys and Rhodes, 1968). The increasr in Km with increasing temperature was attributed to an increase in micellar size, as the cloud point temperature of the surfactant is approached (Humphreys and Rhodes, 1968). 

Marszall (1988) studied the effect of electrolytes on the cloud point of mixed ionic-nonionic surfactant solutions such as SDS and Triton X-100. It was found that the cloud point of the mixed micellar solutions is drastically lowered by a variety of electrolytes at considerably lower concentrations than those affecting the cloud point of nonionic surfactants used alone. The results indicate that the factors affecting the cloud point phenomena of mixed surfactants at very low concentrations of ionic surfactants and electrolytes are primarily electrostatic in nature. The change in the original charge distribution of mixed micelles at a Lxed SDS-Triton X-100 ratio (one molecule per micelle), as indicated by the cloud point measurements as a function of electrolyte concentration, depends mostly on the valency number of the cations (counterions) and to some extent on the kind of the anion (co-ion) and is independent of the type of monovalent cation. 

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