Upper critical solutions temperature

Polymer pairs that appear to have high temperature miscibility although immiscible at or below room temperature (upper critical solution temperature [UCST] behavior). 

It should be noted that the modern view is that all partially miscible liquids should have both a lower and upper critical solution temperature so that all such systems really belong to one class. A closed solubility curve is not obtain in all cases because the physical conditions under normal pressure prevent this. Thus with liquids possessing a lower C.S.T., the critical temperature (the critical point for the liquid vapour system for each component, the maximum temperature at which liquefaction is possible) may be reached before the consolute temperature. Similarly for liquids with an upper C.S.T., one or both of the liquids may freeze before the lower C.S.T. is attained. 

A few systems with both lower and upper critical solution temperatures are tabulated below., ... 

Fig. 1. Phase diagram for mixtures (a) upper critical solution temperature (UCST) (b) lower critical solution temperature (LCST) (c) composition dependence of the free energy of the mixture (on an arbitrary scale) for temperatures above and below the critical value.

The Class I binary diagram is the simplest case (see Fig. 6a). The P—T diagram consists of a vapor—pressure curve (soHd line) for each pure component, ending at the pure component critical point. The loci of critical points for the binary mixtures (shown by the dashed curve) are continuous from the critical point of component one, C , to the critical point of component two,Cp . Additional binary mixtures that exhibit Class I behavior are CO2—/ -hexane and CO2—benzene. More compHcated behavior exists for other classes, including the appearance of upper critical solution temperature (UCST) lines, two-phase (Hquid—Hquid) immiscihility lines, and even three-phase (Hquid—Hquid—gas) immiscihility lines. More complete discussions are available (1,4,22). Additional simple binary system examples for Class III include CO2—hexadecane and CO2—H2O Class IV, CO2—nitrobenzene Class V, ethane—/ -propanol and Class VI, H2O—/ -butanol. 

We consider a binary liquid mixture of components 1 and 3 to be consistent with our previous notation, we reserve the subscript 2 for the gaseous component. Components 1 and 3 are completely miscible at room temperature the (upper) critical solution temperature Tc is far below room temperature, as indicated by the lower curve in Fig. 27. Suppose now that we dissolve a small amount of component 2 in the binary mixture what happens to the critical solution temperature This question was considered by Prigogine (P14), who assumed that for any binary pair which can be formed from the three components 1, 2 and 3, the excess Gibbs energy (symmetric convention) is given by... 

For example, 0 describes the temperature dependence of composition near the upper critical solution temperature for binary (liquid + liquid) equilibrium, of the susceptibility in some magnetic phase transitions, and of the order parameter in (order + disorder) phase transitions. 

Figure 8.17 Vapor fugacity for component 2 in a liquid mixture. At temperature T, large positive deviations from Raoult s law occur. At a lower temperature, the vapor fugacity curve goes through a point of inflection (point c), which becomes a critical point known as the upper critical end point (UCEP). The temperature Tc at which this happens is known as the upper critical solution temperature (UCST). At temperatures less than Tc, the mixture separates into two phases with compositions given by points a and b. Component 1 would show similar behavior, with a point of inflection in the f against X2 curve at Tc, and a discontinuity at 7V...

Point c is a critical point known as the upper critical end point (UCEP).y The temperature, Tc, where this occurs is known as the upper critical solution temperature (UCST) and the composition as the critical solution mole fraction, JC2,C- The phenomenon that occurs at the UCEP is in many ways similar to that which happens at the (liquid + vapor) critical point of a pure substance. For example, at a temperature just above Tc. critical opalescence occurs, and at point c, the coefficient of expansion, compressibility, and heat capacity become infinite. 

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. 

Using the estimated interaction parameters phase equilibrium computations were performed. It was found that the EoS is able to represent the VL2E behavior of the methane-n-hexane system in the temperature range of 198.05 to 444.25 K reasonably well. Typical results together with the experimental data at 273.16 and 444.25 K are shown in Figures 14.14 and 14.15 respectively. However, the EoS was found to be unable to correlate the entire phase behavior in the temperature range of 195.91 K (Upper Critical Solution Temperature) and 182.46K (Lower Critical Solution Temperature). 

Figure 9 Qualitative phase diagram of a polymer solution showing phase separation both on heating (at the lower critical solution temperature) and on cooling (at the upper critical solution temperature). (From Ref. 31.)...

UOP FCC unit, 11 700-702 UOP/HYDRO MTO process, 18 568 UOP Olex olefin separation process, 17 724 Up-and-Down Method, 25 217 U/Pb decay schemes, 25 393-394 Updraft sintering, 26 565 Upflow anaerobic sludge blanket (UASB) in biological waste treatment, 25 902 Upgraded slag (UGS), 25 12, 33 Upland Cotton, U.S., 8 13 U-Polymer, 20 189 Upper critical solution temperature (UCST), 20 320, 322 Upper explosive limit (UEL), 22 840 Upper flammability limit, 23 115 Upper flammable limit (UFL), 22 840 Upper Freeport (MVB) coal... 

Note A miscibility gap is observed at temperatures below an upper critical solution temperature (UCST) or above the lower critical solution temperature (LCST). Its location depends on pressure. In the miscibility gap, there are at least two phases coexisting. 

Note 1 Below the LCST and above the upper critical solution temperature (UCST), if it exists, a single phase exists for all compositions. 

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