Critical-temperature cloud point

Figure 7 Precipitation temperatures (cloud points) vs. composition for polyisobutylene fractions with the indicated number average molecular weights in diisobutyl ketone. Dashed curves are Flory-Huggins binodals with parameters u and determined from a plot of the measured critical points according to equation (158). The dotted curves are the corresponding Flory-Huggins spinodals (reproduced by permission of Wiley, from J. Polym. ScL, Polym. Symp., 1976, 54, 62)...

The aqueous micellai solutions of some surfactants exhibit the cloud point, or turbidity, phenomenon when the solution is heated or cooled above or below a certain temperature. Then the phase sepai ation into two isotropic liquid phases occurs a concentrated phase containing most of the surfactant and an aqueous phase containing a surfactant concentration close to the critical micellar concentration. The anionic surfactant solutions show this phenomenon in acid media without any temperature modifications. The aim of the present work is to explore the analytical possibilities of acid-induced cloud point extraction in the extraction and preconcentration of polycyclic ai omatic hydrocai bons (PAHs) from water solutions. The combination of extraction, preconcentration and luminescence detection of PAHs in one step under their trace determination in objects mentioned allows to exclude the use of lai ge volumes of expensive, high-purity and toxic organic solvents and replace the known time and solvent consuming procedures by more simple and convenient methods. 

The critical point (Ij of the two-phase region encountered at reduced temperatures is called an upper critical solution temperature (UCST), and that of the two-phase region found at elevated temperatures is called, perversely, a lower critical solution temperature (LCST). Figure 2 is drawn assuming that the polymer in solution is monodisperse. However, if the polymer in solution is polydisperse, generally similar, but more vaguely defined, regions of phase separation occur. These are known as "cloud-point" curves. The term "cloud point" results from the visual observation of phase separation - a cloudiness in the mixture. 

An interesting family of polymeric ligands show inverse temperature dependence of solubihty in water, i.e. they can be precipitated from aqueous solutions by increasing the temperature above the so-called cloud point. Typically these ligands contain poly(oxyalkylene) chains, but the phenomenon can be similarly observed with poly(N-isopropyl acrylamide) derivatives (e.g. 132) and methylated cyclodextrins, too. At or above their cloud points these compounds fall off the solution, due to the break-up and loss of the hydration shell which prevents aggregation and precipitation of their molecules. Conversely, upon cooling below this temperature (also called the lower critical solution temperature, LCST) these substances dissolve again. 

Many different types of interaction can induce reversible phase transitions. For instance, weak flocculation has been observed in emulsions stabilized by nonionic surfactants by increasing the temperature. It is well known that many nonionic surfactants dissolved in water undergo aphase separation above a critical temperature, an initially homogeneous surfactant solution separates into two micellar phases of different composition. This demixtion is generally termed as cloud point transition. Identically, oil droplets covered by the same surfactants molecules become attractive within the same temperature range and undergo a reversible fluid-solid phase separation [9]. 

Lower Critical Solution Temperatures LCSTs were determined from plots of optical density at 600 nm versus temperature for 0.03% solutions of each polymer in PBS and were defined as the temperature at which Asoo = 0.1. Temperatures were raised at less than 0.3 C per minute and were measured with a thermometer that had been calibrated against an NBS primary standard thermometer. LCSTs for Figure 6 were determined from the cloud points of 0.01% solutions. 

On the left-hand side of Fig. 4 we have the normal phase diagram of the binary BE-H2O system. The addition of DEC shifts the two phase equilibria to higher BE concentrations and to lower temperatures. If the addition of a third component is continued beyond the cloud point, eventually three distinct phases appear. Unfortunately the cloud point technique gives us the initial concentration or temperature where unmixing begins but is not suitable to distinguish between the coexistence of two phases and three phases. Also the three phase region depends quite critically on temperature. 

The cloud point is close to, but not necessarily equal to the lower consolute solution temperature for polydisperse nonionic surfactants (97). These are equal if the surfactant is monodisperse. Since the lower consolute solution temperature is like a critical point for liquid—liquid mixtures, the dilute and coacervate phases have the same composition, and the volume fraction of solution which the coacervate comprises is a maximum at this temperature (98). If a coacervate phase containing a high concentration of surfactant is desired, the solution should be at a temperature well above the cloud point. 

The cloud point phenomena as a lower consolute solution temperature is becoming better understood in terms of critical solution theory and the fundamental forces involved for pure nonionic surfactant systems. However, the phenomena may still occur if some ionic surfactant is added to the nonionic surfactant system. A challenge to theoreticians will be to model these mixed ionic/nonionic systems. This will require inclusion of electrostatic considerations in the modeling. 

The cloud point curves of the epoxy monomer/PEI blend and BPACY monomer/PEI blend exhibited an upper critical solution temperature (UCST) behavior, whereas partially cured epoxy/PEI blend and BPACY/PEI blend showed bimodal UCST curves with two critical compositions, ft is attributed to the fact that, at lower conversion, thermoset resin has a bimodal distribution of molecular weight in which unreacted thermoset monomer and partially reacted thermoset dimer or trimer exist simultaneously. The rubber/epoxy systems that shows bimodal UCST behavior have been reported in previous papers [40,46]. Figure 3.7 shows the cloud point curve of epoxy/PEI system. With the increase in conversion (molecular weight) of epoxy resin, the bimodal UCST curve shifts to higher temperature region. 

Further heating led to liquid-liquid phase separation observed as a cloud point. This is an example of LCST (lower critical solution temperature) behavior. 

Trichlorodifluoroethane (HCFC-122) is a co-spin agent, which lowers the cloud-point pressure. The cloud-point pressure means the pressure at which a single phase liquid solution begins to phase separate. At temperatures above the critical point, there cannot be any liquid phase present and therefore a single phase, supercritical solution phase separates into a polymer-rich/spin fluid-rich, two-phase gaseous dispersion. 

Studies on non-ionic surfactants as effective drag-reducing additives have been submitted by Zakin (1972). He studied various effects on three non-ionic surfactants formed from straight-chain alcohols and ethyleneoxide. These surfactants have an upper and a lower temperature limit for solubility in water and prove effective drag reducers near their upper critical solubility temperature or clouding point. The clouding point is the point at which a solution of a non-ionic agent in water becomes turbid as the temperature is raised. 

Lower Critical Solution Temperature and Cloud Point. 343... 

There are some similarities between third-phase formation in liquid/liquid extraction and the critical phenomenon of cloud points in aqueous solutions of nonionic polyethoxylated surfactants (12, 91). When a nonionic micellar solution is heated to a certain temperature, it becomes turbid, and by further increasing the temperature,... 

Figure 8.2 Schematic phase diagrams for thermoplastic-epoxy monomer (diglycidyl ether of bisphenol A) blends, (CPC = cloud point curve, and VC = vitrification curve), (a) and (b) UCST (upper critical solution temperature) behaviour for PPE and PEI (respectively) - DGEBA n = 0.15 (c) LCST (lower critical solution temperature) behaviour for PES-DGEBA y n = 0.15. (Pascault and Williams, 2000 - Copyright 2001. Reprinted by permission of John Wiley Sons Inc.)...

A plot of the temperatures required for clouding versus surfactant concentration typically exhibits a minimum in the case of nonionic surfactants (or a maximum in the case of zwitterionics) in its coexistence curve, with the temperature and surfactant concentration at which the minimum (or maximum) occurs being referred to as the critical temperature and concentration, respectively. This type of behavior is also exhibited by other nonionic surfactants, that is, nonionic polymers, // - a I k y I s u I Any lalcoh o I s, hydroxymethyl or ethyl celluloses, dimethylalkylphosphine oxides, or, most commonly, alkyl (or aryl) polyoxyethylene ethers. Likewise, certain zwitterionic surfactant solutions can also exhibit critical behavior in which an upper rather than a lower consolute boundary is present. Previously, metal ions (in the form of metal chelate complexes) were extracted and enriched from aqueous media using such a cloud point extraction approach with nonionic surfactants. Extraction efficiencies in excess of 98% for such metal ion extraction techniques were achieved with enrichment factors in the range of 45-200. In addition to metal ion enrichments, this type of micellar cloud point extraction approach has been reported to be useful for the separation of hydrophobic from hydrophilic proteins, both originally present in an aqueous solution, and also for the preconcentration of the former type of proteins. 

As an impressive phase study, it was observed that a blend system composed of CAB having 54 mol % butyryl side groups and polyfethylene oxide) (PEO Mn = 35 000) yielded a phase diagram with a lower critical solution temperature (LCST) boundary, and a cloud point of 168 °C at the critical composition of CAB/PEO = 40/60 (w/w) [112]. 

The wetting of a liquid drop placed on a solid surface has already been described (Section 3.4) by the critical surface tension of the surface and by Young s equation. Temperature is a factor in wetting by aqueous solutions since it influences surfactant solubility. For example, the fastest wetting for polyoxyethylenated non-ionic surfactants is produced by those whose cloud points are just above the use temperature [193]. 

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