Lecture34 Wed Dec 6

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5.

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5C.4 Liquid-solid phase diagrams


The temperature composition phase diagram For 2-component systems in which the liquids are
miscible in all proportions, but the solids are immiscible in all proportions, looks like

5C.4(a) Eutectics
Consider cooling of a liquid of composition a1:
- a1 → a2: pure solid B comes out of the liquid, which becomes richer in A
- a2 → a3: more solid B forms, and the relative amounts of the solid a liquid (which are in
equilibrium) are given by the lever rule
- a3 → a4: at the end of this step, there is less liquid than at a3 and its composition is given by e2.
Infinitessimally below a4, liquid then freezes and you have a two-phase mixture of
A(s) and B(s)

Eutectic point (curve crossing):


- solution of A(s) and B(s) with the lowest melting point (or freezing points of A(l)
and B(l) are identical)
- both A and B will freeze out at a single temperature if T is lowered, i.e., with
previously depositing pure A(s) or pure B(s)
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- The solid aggregate of A(s) and B(s) with the eutectic composition will have a constant
melting point just like a pure solid does.

5C.4 (b) Reacting systems


Many binary systems react to produce compounds. Example where A and B form compound
C=AB

Consider cooling of a liquid of composition a1, i.e., a system that consists of C and unreacted B
(mixed A with excess B):
- a1 → a2: pure solid C=AB comes out of the liquid, which becomes richer in B
- a2 → a3: more solid C=AB forms, and the relative amounts of the solid and liquid
(which are in equilibrium) are given by the lever rule
- a3 → a4: at the end of this step, there is less liquid than at a3 and its composition is
given by e. Infinitessimally below a4, liquid then freezes and you have a
two-phase mixture of C(s) and B(s)


5C.4(c) Incongruent melting


In some cases, compound C is not stable as a liquid, e.g., Na2K
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Consider cooling of a liquid of composition a1, i.e., a system that consists of Na and K:
- a1 → a2: pure solid A solid solution rich in Na (containing some K) comes out of the
liquid, which becomes richer in K
- a2 → just below a3: solid solution rich in Na (with some K) and Na2K

Question: Label the regions of the phase diagram shown below. State what substances (if
compounds give their formulae) exist in each region. Label each substance in each region as
solid, liquid, or gas. (b) What phases, and how much of each phase, would be present if 10.0
moles sample with xB = 0.2 what heated to the melting temperature of the eutectic with xB=
0.45?

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