Class 4.

2
More Colligative Properties,
Solutions & Distillation

CHEM 102H
T. Hughbanks

Boiling point elevation and

freezing point depression
 When nonvolatile solutes are present in a
solvent, the solution’s boiling point rises and
freezing point declines.
 For very dilute solutions, these effects
depend only on what the solvent is and the
the solute concentration.
 The origin of this behavior is basically the
same as the origin of osmotic pressure.

Entropy of the solute “gas” decreases

when volume decreases in vaporization

V V–Vm

n moles of solute molecules are forced into the

decreased solvent volume when a mole of solvent
leaves (Vm = volume of a mole of solvent).
∆Ssolute = nRln[(V-Vm)/V] = nRln[1 - (Vm/V)]
Since V >> Vm, ln[1 - (Vm/V)] ≈ - Vm/V
∆Ssolute = - nR(Vm/V) = - (n/V)RVm
 Total Entropy of vaporization is less for
the solution than for the pure solvent
∆Svap,soln = ∆Svap,pure + ∆Ssolute (∆Ssolute < 0)
Tb,soln = ∆Hvap,pure/∆Svap,soln - for dilute solution
= ∆Hvap,pure/[∆Svap,pure + ∆Ssolute]
≈ [∆Hvap,pure/∆Svap,pure ][1 - (∆Ssolute/∆Svap,pure)]
= Tb,pure - Tb,pure(∆Ssolute/∆Svap,pure)
Therefore,
Tb,soln = Tb,pure + Tb,pure[(n/V)RVm/∆Svap,pure]

Boiling point elevation

Tb,pure[(n/V)RVm/∆Svap,pure]
L solvent n mol solute
Vm = ; =
mol solvent V L solution
n mol solute mol solute kg solvent
V ! = "
V m mol solution kg solvent mol solvent
M
= m • solvent ; where m is the molality
1000
(Msolvent/1000)[RTb,pure/∆Svap,pure] × m
(Msolvent/1000)[RT2b,pure/∆Hvap,pure] × m

Calculated and Observed kb’s

Boiling !H˚vap
Solvent point at 1 kJ/mol Calc. Obs.
atm, K
Water 373.2 40.67 0.513 0.51
(CH3)2CO 329.3 30.46 1.72 1.72
CCl4 349.9 30.00 5.22 4.9
CH3Cl 334.4 29.37 3.78 3.9
CH3CH2OH 351.7 38.58 1.23 1.20
CH3OH 337.9 35.27 0.86 0.84
(CH3CH2)2O 307.6 27.66 2.11 2.16
C6H6 353.3 30.75 2.63 2.6
 Freezing point depression
Tf,pure[(n/V)RVm/∆Sfus,pure]

(Msolvent/1000)[RT2f,pure/∆Hfus,pure] × m

Note: On p. 307, it states that “the freezing point

constant of the solvent…is different for each solvent
and must be determined experimentally” This is true,
but it doesn’t mean that it isn’t theoretically
predictable from other properties of the solvent, as
this equation’s derivation shows.

Boiling point elevation and

freezing point depression

Raoult’s Law
 The vapor pressure, P, of a solvent over a
solution (with a nonvolatile solute) is
proportional to the solvent mole fraction,
xsolvent:
P = xsolventPpure
 Like the colligative properties already
discussed, this can be shown by considering
the change in entropy associated with the
presence of the solute.
 Applies well to dilute solutions and to certain
concentrated “ideal” solutions.
 Derivation of Raoult’s Law
liq(soln ) gas
- RT ln K = - RT ln P = ΔGvap = ΔHvap - TΔSvap
For the solution, ΔSvap = ΔSvap,pure + ΔSsolute
For a dilute solution, ΔHvap = ΔHvap,pure
Therefore,
-RT ln P = ΔHvap,pure - TΔSvap,pure - TΔSsolute
-RT ln P = -RT ln Ppure - TΔSsolute
-RT ln (P/Ppure) = - nRTln[1 - (Vm/V)]
ln (P/Ppure) = ln[1 - (Vm/V)]n

Derivation of Raoult’s Law, cont.

liq(soln ) gas
(P/Ppure) = [1 - (Vm/V)]n
(P/Ppure) ≈ [1 - n(Vm/V)] = [1 - (n/V)Vm]
n/V = (mol solute)/(L solution)
Vm = (L solvent)/(mol solvent)
1 - (n/V)Vm ≈ (mol solute)/mol(solute + solvent)
(P/Ppure) = xsolvent
P = xsolventPpure

Example
(a) Calculate the vapor pressure of water over
a solution prepared by dissolving 10.0 g of
glucose (C6H12O6) in 100 g of water.
(b) Sucrose is a disaccharide formed by
“condensation” of one molecule of glucose
and one molecule of fructose. Will the
vapor pressure of water of a solution made
from 10.0 g of sucrose and 100 g H2O be
greater or less than the in the case of
glucose?
 Binary Liquid Mixtures
 When a mixture of two
liquids, A and B, both
obey Raoult’s Law
(ideal mixture), the
vapor pressures of each
gas over the solution are:
PA = xA,liquidPA,pure
PB = xB,liquidPB,pure

Binary Liquid Mixtures

Ptotal = PA + PB = xA,liquidPA,pure + xB,liquidPB,pure
 The gas phase mole fractions are:
xA,gas = PA/(PA + PB); xB,gas = PB/(PA + PB)
xA,gas = xA,liquidPA,pure /(xA,liquidPA,pure + xB,liquidPB,pure)
xB,gas = xB,liquidPB,pure /(xA,liquidPA,pure + xB,liquidPB,pure)
 “A” is more volatile, “B” is less volatile (i.e.,
PA,pure > PB,pure). Do some basic algebra:
xA,gas = xA,liquid /[xA,liquid + xB,liquid(PB,pure/PA,pure)]
xB,gas = xB,liquid /[xA,liquid(PA,pure/PB,pure) + x B,liquid]

Binary Liquid Mixtures, cont.

 Remember, xA,liquid + xB,liquid = 1
xA,liquid + xB,liquid(PB,pure/PA,pure) < 1
xA,gas > xA,liquid
xA,liquid(PA,pure/PB,pure) + xB,liquid > 1
xB,gas < xB,liquid
 The vapor is richer in the more volatile A -
as we would expect!
 Ideal Binary Liquid Behavior

“A” is more
volatile than “B”
(PA,pure > PB,pure)

xA,liquid + xB,liquid = 1
xA,gas > xA,liquid
xB,gas < xB,liquid

Distillation
This figure (from text)
shows how the vapor
phase is richer in the
volatile benzene (b.p.
80.1) in a mixture with
toluene (b.p. 110.6).
Note that if the vapor
mixture is condensed it
would boil at lower T.

Fractional
Distillation
Successive distillations
give vapor fractions
that are increasingly
rich in the volatile
component, benzene
(b.p. 80.1) in a mixture
with toluene (b.p.
110.6).
ΔHmix > 0
Non-ideal
Behavior;
Azeotropes
When the interactions
between solute and solvent
molecules are dissimilar,
Raoult’s Law doesn’t apply
(ΔHmix ≠ 0).
Negative deviations from
Raoult’s Law are seen in
this low-boiling azeotrope.