About determination of partial molar volume

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About determination of partial molar volume nB Measurement M(CuSO4)/g 5 10 15 20 ρ/g.cm-3 1.051 1.107 1.167 1.230 V/cm-3 99.90 99.37 98.54 97.56 Method 1 Method 2 α W2% α1 α2

Measurement of saturated vapour pressure External pressure Pressure

5.4.2 Phase diagrams of partly miscible binary systems Extraction technique Φmin=1, Fmax=3 ( )p, T,X 313K 363K 373K critical consolute temperature ( the upper…) Φ=2, F=2-2+1 ()T

Example Mixture of 50g of hexane (0.59mol) and 50g of nitrobenzene (0.41mol), 290K. Questions: (1) the compositions of the phases; (2) To what temperature the sample be heated in order to obtain a single phase? T=290K, horizontal tie line xhexane=0.35; lα xnitrobenzene=0.83; lβ Tc=292K

Why two phases coexisting : the thermodynamic basic principle ΔmixG = nRT(xA ln xA + xB ln xB + βxAxB) GE = nβRTxAxB The location of the phase boundary on the basis of the βparameter Interpretation about the lever rule

H2O-triethylamine (C2H5)3N 291.2K The lower critical solution temperature

H2O-nicotinamide 481K 334 K Upper and lower critical consolute temperatures

H2O-ethyl ether No critical consolute temperature

Inferring according to the phase diagram Higher temperature range Phase state variation following path a1-a2: L - L+G - G Low-boiling azeotrope Phase state variation following path b2-b1: L1+L2 – L - L+G -G Partly miscible in liquid solution Partly miscible in liquid solution How about b1-b2 ?

T-x phase diagram for a binary system Phase state variation following path a1—a2: e1-e2 b1-b2: F=2-1+1=2 F=2-2+1=1 F=2-3+1=0 F=2-1+1=2 F=2-2+1=1 Boiling occurs before the two liquids are fully miscible

Example State the changes that occur when a mixture of composition xB=0.95 0.62:1 0.82:1

5.4.3 Immiscible systems L1 L2 G incapable of mixing

F=2-3+1=0 T=90℃ P=9.79X104Pa A(l)+B(l) b a g T P g+B(l) g+B(l) g A(l)+g g+B(l) g+B(l) A(l)+g g A(l)+B(l) H2O C6H5Cl H2O C6H5Cl

Water vapour distillation

5.4.4 Phase diagrams of Liquid-solid binary systems a1-a5: b F=2-3+1=0 Path b: EutecticsxB

5.4.4.1 Water-salt system

Application Consolute temperature Water-salt 252 K 218 K 262.5 K

Homework Y: P166 22; P169:25 A: P216 8.13(a) 8.17(a) P218 8.2 Preview: