Non-ideal solutions

Strong deviations from

ideality are shown by
dissimilar substances Raoults law
obeyed for a
close-to-pure
solvent

William Henry
(1775-1836)
observed
Henrys law (for
a dilute solute):
pB = xBKB (e.g., gas solubility)
Nils Walter: Chem 260

Ideal and real solutions: Activities

From both Raoults (solvent) and
Henrys laws (solute) follows:
O
solv (l ) = solv
(l ) + RT ln xsolv
O
(l ) + RT ln C[ solv ]
= solv
O

J
J + RT ln[J ]

standard chemical
potential @ 1 M
The chemical potential is a
measure of the ability of J
to bring about physical or
chemical change

BUT:

to
preserve
equation
for real
solutions:

J = OJ + RT ln a J
Effective concentration
= activity aJ = J[J]
Nils Walter: Chem 260

Consequences of chemical potential changes

in mixtures: Colligative properties
Freezing point depression:
Tf = KfbB

Boiling point elevation:

TB = KBbB

cryoscopic constant

Solute is insoluble
in solid solvent:

ebullioscopic constant

molality

Solute is not
volatile:
Chemical
Potential
lowered by
solute

Chemical
Potential
lowered by
solute

Nils Walter: Chem 260

Phase diagrams of binary mixtures

Phase rule: F = C - P + 2
p = constant:

p,T

for binary mixtures = 2

Temperature-composition diagram
for binary mixture of volatile liquids

in
equilibrium

Nils Walter: Chem 260

Finally, as promised: Whisky distillery

Fractional distillation:

Non-ideal mixtures
High-boiling azeotrope,
e.g., nitric acid/water

Low-boiling azeotrope,
e.g., ethanol/water

Nils Walter: Chem 260

Liquid-liquid phase diagrams of

partially miscible liquids
E.g., hexane/nitrobenzene:
Upper critical
solution
temperature
(thermal motion)

E.g., triethylamine
/water:

Lever rule

Lower Tcrit
(complex formed)

Amount of phase of composition a" l '

Nils Walter: Chem 260 =
Amount of phase of composition a' l"