Practical Physical Chemistry

Solutions Chemistry and

Chemical Equilibrium
Second Semester
2020-2021
Department of Chemistry
Second year

Aveen AL-Saka
 Lab (5)
Liquid and solid phase
diagram for two
components
2
3
No solid solution are formed, eg. .Bi and
-:Cd, salts and water
These are simple eutectic systems. The freezing
point of a solution is lower than that of a pure
liquid. Which component is designated the
solvent is arbitrary. We thus obtain two freezing
point curves for solutions of C in B and vice
.versa, which meet at the eutectic point

4
 For a salt in water one curve is usually called the
freezing point curve (liquid in equilibrium with
solid water) and the other the solubility curve
.(liquid in equilibrium with salt)

On cooling a liquid it separates into two phases

one solid and one liquid at the freezing point e.g.
at T1below. On reaching T2, S2 gives the
composition of the solid phase (pure C) in
equilibrium with liquid L2, the overall
composition must of course remain as y. the lines
.S2L2 etc. are called tie lines
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 Two-component solid-liquid equilibrium
Liquid-phase miscibility and solid-phase immiscibility

TB* TC* Freezing points of B & C

T Fig.1
R
Curve AE A TC* S1 L1
Freezing-point-depression curve of T1 liquid solution (l.s.)
C due to solute B of B+C
S2 H D
L2
Curve DE T2 TB*
l.s.+C(s)
Freezing-point-depression curve of l.s.
B due to solute C K E
+B(
T3=Te M
Ns)
Point E The eutectic point S solid B+solid C
T3 =Te The eutectic temperature
0 y xB'' Ce 1
B
Simple eutectic system C xB
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 Experimental Methods

Cooling curves
℃/ T

T Last of 4
Halt point liquid
removed 3
Teu

t 2
1
T Break point
Last of
Tb Halt point
liquid
Teu removed
t/s

t 7
On reaching Te some liquid still remains. However no liquid
can exist in equilibrium below this temperature, hence
solidification becomes complete at this temperature and the
rest of the solid formed has composition Ce the eutectic
mixture. The behavior of mixture Ce on cooling resembles
that of a pure substance (fig 2). The eutectic has no special
composition however and is merely a mixture of C and B.
.the line AED is the liquidus CMENB the solidus
:Cooling curves
A liquid mixture of composition C is cooled. Below the
freezing point T1 the rate of cooling decreases since as solid
C separates its enthalpy of fusion is liberated. Super –
cooling will probably occur to some extent. Followed by
sudden crystallization of part of solute C thus restoring
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.equilibrium
This result in a kink in the cooling curve (fig 3). To obtain the
temperature at which crystallization would have commenced if
these has been no super cooling the linear portion is
extrapolated back as shown. The composition of the liquid
changes along the liquidus AE, finally at temperature Te
attaining the eutectic composition (fig.2). It must then solidify
at constant temperature. The solid then cools. From cooling
curves of mixtures of known composition the liquidus and
.solidus can thus be constructed

Fig.3
9 Fig.2
T/

℃
80 ）l(A+B TB
c

60

40 l (A+B ） +
）s(A)+l(A+B
TA s(B)

20

C E s(A)+s(B) D

0.0 0.2 0.4 0.6 0.8 1.0

)A（ xB ) B（

Phase diagram
℃/ T ℃/ T xB=1.0
T/ *
T xB=0.867 82.15

℃
•
B
80 ）l(A+B
e 72.27
•
Ⅶ
xB=0.685
d
•
60 57.89 Ⅵ
xA=1.0
xB=0.229 xB=0.417
xB=0.329 l (A+B ） +sB
Ⅰ 40 ）s(A)+l(A+B
Ⅱ Ⅲ
•
*
T c 28.50 Ⅴ
32.09 20.75
14.85
A
20
a
••b • • Ⅳ

•C 'a bE•'c 'd e D

14.65 14.65 s(A)+s(B) 14.65 14.65 14.65
' '
t/s 0.0 0.2 0.4 0.6 0.8 1.0 t/s
) A（ xB )B（

Cooling curves Phase diagram Cooling curves

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