Non-ideal solutions

Strong deviations from

ideality are shown by
dissimilar substances Raoult’s law
obeyed for a
close-to-pure
solvent

William Henry
(1775-1836)
observed
Henry’s law (for
a dilute solute):
pB = xBKB (e.g., gas solubility)
Nils Walter: Chem 260
 Ideal and real solutions: Activities
From both Raoult’s (solvent) and
Henry’s laws (solute) follows: BUT:

µ solv (l ) = µ solv
O
(l ) + RT ln xsolv
= µ solv
O
(l ) + RT ln C[ solv ] ß
to
µ
Þ J = µ O
J + RT ln[J ] preserve
equation
standard chemical for real
potential @ 1 M solutions:

The chemical potential is a µ J = µOJ + RT ln a J

measure of the ability of J Effective concentration
to bring about physical or = activity aJ = γJ[J]
chemical change Nils Walter: Chem 260
Consequences of chemical potential changes
in mixtures: Colligative properties
Freezing point depression: Boiling point elevation:
∆Tf = KfbB ∆TB = KBbB
cryoscopic constant ebullioscopic constant
molality
Solute is insoluble Solute is not
in solid solvent: volatile:

Chemical
Potential
lowered by
solute

Chemical
Potential
lowered by
Nils Walter: Chem 260
solute
Phase diagrams of binary mixtures
Phase rule: F = C - P + 2 p,T
p = constant: for binary mixtures = 2
Temperature-composition diagram
for binary mixture of volatile liquids

in
equilibrium

Nils Walter: Chem 260