Upper critical solution temperature
The upper critical solution temperature (UCST) or upper consolute temperature is the critical temperature above which the components of a mixture are miscible in all proportions. The word upper indicates that the UCST is an upper bound to a temperature range of partial miscibility, or miscibility for certain compositions only. For example, hexane-nitrobenzene mixtures have a UCST of 19 °C, so that these two substances are miscible in all proportions above 19 °C but not at lower temperatures. Examples at higher temperatures are the aniline-water system at 168 °C (at pressures high enough for liquid water to exist at that temperature), and the lead-zinc system at 798 °C (a temperature where both metals are liquid).
A solid state example is the palladium-hydrogen system which has a solid solution phase (H2 in Pd) in equilibrium with a hydride phase (PdHn) below the UCST at 300 °C. Above this temperature there is a single solid solution phase.
The phase separation at the UCST is in general driven by unfavorable energetics; in particular, interactions between components favor a partially demixed state.
Some polymer solutions also have a lower critical solution temperature (LCST) or lower bound to a temperature range of partial miscibility. As shown in the diagram, for polymer solutions the LCST is higher than the UCST, so that there is a temperature interval of complete miscibility, with partial miscibility at both higher and lower temperatures.
By adding soluble impurities the upper critical solution temperature increases and lower critical solution temperature decreases.
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- P.W. Atkins and J. de Paula, "Atkins' Physical Chemistry" (8th edn, W.H. Freeman 2006) p. 185
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- Atkins and de Paula p. 186
- Sanchez, IC and Stone, MT, "Statistical Thermodynamics of Polymer Solutions and Blends" in Polymer Blends Volume 1: Formulation. Edited by D.R. Paul and C. B. Bucknall, 2000 John Wiley & Sons, Inc.
- Cowie, J.M.G. "Polymers: Chemistry and Physics of Modern Materials" (2nd edn, Blackie 1991) pp. 174–176
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