5.8 Liquid-Liquid phase diagrams - Sogang OCW（5.8液-液相图西江OCW）.pdf

5.8 Liquid-Liquid phase diagrams Key points 1.  Phase separation of partially miscible liquids may occur when T is below UCST or above LCST 2.  UCST is the highest T at which phase separation occurs. LCST is the lowest T at which phase separation occurs 3.  The outcome of a distillation of a low-boiling azeotrope depends on whether the liquids become fully miscible before they boil or boiling occurs occurs before mixing is complete 4.  Consider partially miscible liquids 5.8 Liquid-Liquid phase diagrams (a) Phase separation •  Suppose a small amount of liquid B is added to a sample of another liquid B at T’. Liquid B dissolves completely forming a single phase •  As more B is added, a stage comes at which no more dissolves. The sample consists of two phases in equilibrium; A-rich phase (a’’) and B-rich phase (a’) •  Lever rule is still applied •  As more B is added, a stage comes at so much B is present and it can dissolve all the A forming a single phase 5.8 Liquid-Liquid phase diagrams (b) Critical solution temperature •  Upper critical solution temperature (UCST) : the highest temperature at which phase separation occurs •  The phase boundary: ∂∆mixG/∂x = 0 x ln +ξ (1− 2x ) = 0 1− x •  Lower critical solution temperature (LCST) : below LCST they mix in all proportions and above which they form two phases •  Some systems have both upper and lower critical solution temperatures (Figure 5.47) 5.8 Liquid-Liquid phase diagrams (c) The distillation of partially miscible liquids •  Consider a pair of liquids that are partially miscible and form a low- boiling azeotrope •  This combination is quite common because both properties reflect the tendency of A and B to avoid each othe