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Effect of solutes on the properties of the solvent

Properties of pure solvents are affected when solutes are


dissolved in the solvent.

The presence of the solute affects the interactions


between solvent molecules
molecules.

COLLIGATIVE properties: properties of solvents which


are affected by the concentration of the solute
Example: boiling point, freezing point, vapor pressure
For dilute solutions, the extent to which these properties of
the p
pure solvent are affected depends
p on the amount of
solute added and not on the type of solute added.

An ideal solution is a homogenous mixture off two or more


components that mix without change in volume or flow of
heat into or out of the system.
y

In an ideal solution all molecules find themselves in an


environment very much like that in the pure solute and
solvent; most ideal solutions are with similar molecules.
Concentrations of solutions

mass of component X 100%


Mass percentage = total mass of mixture

moles of component
Mole fraction = total number of moles in mixture

moles of solute
molarity (M) = = mol L-1
liter of solution

moles of solute
molality (m) = = mol kg-1
kilogram of solvent
Effect of solute on vapor pressure

Consider an ideal solution of a volatile solvent with a non-


volatile solute.

Since the solvent is volatile, but not the solute, the vapor
pressure above the solution is due to the solvent only.
only

The vapor pressure of the solution is LOWER than the vapor


pressure of the pure solvent.

Experiments indicate that, for ideal solutions, the vapor


pressure of the solution is directly proportional to the mole
fraction of the solvent in the solution.
If P1 is the vapor pressure of the solution, P1o the vapor
pressure of the pure
p p solvent,, and X1 the mole fraction of the
solvent in the solution,then:

P1 = X1 P1o Raoults
Raoult s Law
Most solutions obey Raoults law at low concentrations of
solute.

Deviations from Raoults law provides information on the


nature of the solute-solvent
solute solvent interactions.
interactions
Relating the lowering of vapor pressure to the
solute concentration

The change in the vapor pressure of the solvent when a


nonvolatile solute is added is:
P1 = P1- Po1

From Raoults Law


P1 = X1Po1 - Po1
= Po1 (X1 - 1)

where X1 is the mole fraction of the solvent


Si
Since X1 + X2 = 1 (X2 is
i the
th mole l fraction
f ti off the
th solute)
l t )
Vapor pressure of solvent above a
P1 = - X2 Po1 dilute solution is always lower than the
pure solvent
Elevation of Boiling Point
Since the equilibrium vapor pressure of the solvent is
lowered when a solute is added, the boiling point of the
solution is raised.
raised

The elevation in boiling , Tb is related to the


g point,
p
concentration of the solute in solution as follows:

Tb = Kb m
where Kb is a constant and m is the MOLALITY of the
solution

Note: Kb depends
p on the solvent,, not on the solute.
What happens if the solute dissociates in solution?
Colligative
C lli i propertiesi depend
d d on the
h number
b off solute
l
molecules in solution

Tb = i Kb m vant Hoff equation


where i equals the number of particles released into
solution per formula unit of solute
i = 2 for
f NaCl;
N Cl i = 3 ffor C
CaCl
Cl2

Note: the vant Hoff equation holds for ideal solutions and
hence for strong electrolytes, Tb calculated using this
equation is typically an upper limit.
limit
Depression of Freezing Point
Addition of solute to a solvent causes its freezing
g point
p to
decrease
(explains why salt is used on icy roads, and a mixture of
ethylene glycol and water works as anti-freeze)
anti freeze )

For dilute solutions of a non-dissociating solute:


Tf = - Kf m
The negative sign indicates a lowering of the freezing
point
Kf is a constant that depends on the solvent and not on
the solute.

For dilute solutions of a dissociating solute:


Tf = - i Kf m
Boiling point and freezing point constants
Estimating degree of dissociation
Osmotic Pressure
Water
W t flows
fl from
f the
th pure solvent
l t side
id to
t the
th solution
l ti
side, because there are more water molecules per unit
volume in the p
pure water side.

The net effect is that the solution becomes more diluted


diluted.

OSMOSIS: If two
OSMOSIS t solutions
l ti off different
diff t concentrations
t ti are
separated by a semi-permeable membrane, the solvent
flows from the side which has a higherg concentration of
solvent to the side with a lower concentration of solvent.
h

=gdh

The pressure that must be applied to the solution side to


exactly
tl stop
t the
th flow
fl off solvent
l t through
th h the
th membrane,
b i.e.
i
stop osmosis, is called the OSMOTIC PRESSURE ().
IIn an ideal
id l solution,
l ti the
th osmoticti pressure obeys
b a
relationship that looks like the ideal gas law:
= n R T/V
Since n/V is the molar concentration (c)
=cRT
For dissociating solutes:
=icRT

Higher the concentration of the solute, higher is the


osmotic pressure required to prevent osmosis.
Since depends
p on the concentration of the solute it is a
colligative property.

Measuring the osmotic pressure can be used to determine


the molar mass of the solute.

For example,
example measuring the osmotic pressure of a
solution containing a protein can be used to estimate the
molar mass of the protein.

= n R T = (mass) R T
V MV
Body fluid ~ 0.15 molal NaCl

b) solution too concentrated


c) solution too dilute
Purification of water - Desalination

Normal osmosis Reverse osmosis


Colligative properties of mixtures

For an ideal solution of two volatile substances


((A & B),
) if each component
p obeys
y Raoults Law:

PA = XAPAo
PB = XBPBo = (1-XA) PBo

The total vapor pressure of the mixture is


determined by Daltons law
Ptot = PA + PB = XAPAo + (1 XA) PBo
(1-X
Separation of a mixture of two volatile compounds

A mixture of two components with different vapor


pressures can separated by FRACTIONAL
DISTILLATION

Because of the different vapor pressure of the


components in the solution, the composition of the
vapor above the solution is not the same as the
solution itself.
Separation of a mixture of hexane (C6H14) and heptane
(C7H14).
Heptane and hexane form a nearly ideal mixture over
the whole range of mole fractions.
At 25oC
Vapor pressure of hexane, P1o = 0.198 atm

Vapor
p pressure
p , P2o = 0.0600 atm
of heptane,
p

Mixture contains 4
4.00
00 mol hexane and 6
6.00
00 mol heptane
From Raoults Law
Phexane = P = X P o = (0.400)(0.198
(0 400)(0 198 atm) = 0
0.0792
0792 atm
h 1 1 1

Pheptane = P2 = X2 Po2 = (0.600)(0.0600 atm) = 0.0360 atm

From Daltons Law


Ptot = P1 + P2 = 0.1152 atm

Mole fraction of hexane in the vapor



0.0792 atm
X1= =0.688
0.1152 atm

Mole fraction of heptane in the vapor


0 0360 atm
0.0360 t

X2= =0.312
0.1152 atm
The vapor is enriched with the more volatile component
(in this example, hexane)
Fractional Distillation separates components in a mixture.
Solution is boiled, and vapors are collected and
condensed.
The solution formed from the condensate is richer in
the more volatile component.
Boiling this solution and condensing the vapors enriches
the resulting condensate with the more volatile
component.