Properties of a solution that differ from those of

the solvent by an amount that depends only on

the number of solute particles, and not on their
nature.
They are:
 Vapor Pressure Lowering

 Boiling point elevation and freezing point

depression
 Osmotic Pressure
As a rule, these are easily predicted for relatively
dilute solutions, i.e. concentrations smaller
than 0.02 M

As they depend on the number of solute particles,

it will be important to keep in mind that many
solutes (called Electrolytes) break down as ions
in solution, either completely (strong) or
partially
 En el caso de electrolitos, será importante
usar el factor de Van’t Hoff (i), que
representa el número t0tal de moles de
partículas en solución formadas por mol de
soluto puesto a disolver.
 Si el electrolito se disocia hasta a%

i=1+a
 El factor de Van’t Hoff varia en general entre 1
y 2, valiendo 1 para un no electrolito como el
agua, y 2 para un electrolito fuerte, como NaCl,
y hasta 3 para una sal cómo K2SO4
 En todas las formulas presentadas en lo que
sigue se deberá sustituir (i . m) por el m escrito
con el fin de calcular las propiedades
coligativas de una disolución de un electrolito.
Mucha gente nombra a las concentraciones
eficaces así calculadas (i . m), como

 Osmolalidad (la molalidad multiplicada por el

factor) y
 Osmolaridad (la molaridad multiplicada por el
factor) .
If the solute is non volatile, the vapor pressure of
its solutions always lower than the one of the
pure solvent at the same temperature.
The vapor pressure of the solvent over the
solution is given by Raoult’s Law:

P1  χ1  P 1
0

Where P1 is the vapor pressure of the solution, c1 is the mole fraction

of the solvent, and P10 the vapor pressure of the pure solvent at the
same temperature
If one looks at the change in the vapor pressure of
the solution (DP1), the role of the solute is more
evident:
ΔP1  χ 2  P 1
0

Where DP1 is the decrease in the vapor pressure of the solution, c2 is the
mole fraction of the solute, and P10 the vapor pressure of the pure
solvent at the same temperature
If both the solute and the solvent are volatile, the
total vapor pressure will be, according to
Dalton’s law, the sum of the vapor pressure of
both components:
Pt  P1  P2  χ 1  P10  χ 2  P20

As an application of this, one can look at fractional

distillation.
Boiling Point Elevation
Can be seen as a direct consequence of the
previous effect:
 The vapor pressure of a liquid increases with the
temperature
 The boiling point is the temperature at which the vapor
pressure reaches the value of the applied pressure
 In the presence of a solute, the vapor pressure is
lowered, needing a higher temperature to reach a given
value.
 Therefore the boiling point is at a higher temperature
in the presence of a solute
The Boiling Point Elevation DTb is equal to the
observed boiling temperature Tb minus the
pure solvent boiling temperature Tb0

It is always a positive value:

ΔTb  Tb  T  k b  m
0
b
Where m is the solute molality, and Ts are measured in kelvin or degrees
Celsius
Very similar to previous, the freezing point
depression DTf is equal to the freezing point of
the pure solvent Tf0 minus the observed one of
the solution Tf
ΔTf  Tf0  Tf  k f  m

Where m is the solute molality, and Ts are measured in kelvin or degrees

Celsius

It is always a positive value

 Normal Kf Normal Kb
Solvent
Freezing Point (°C/m) Boiling Point (°C/m)

Water 0 1.86 100 0.52

Benzene 5.5 5.12 80.1 2.53

Ethanol -117.3 1.99 78.4 1.22

Acetic Acid 16.6 3.90 117.9 2.93

Cyclohexane 6.6 20 80.7 2.79

Osmotic Pressure
When a semi permeable membrane (that allows
the passage of only some molecules, according,
for instance, to size) is used to separate two
compartments containing solutions of different
concentration, the phenomenon of Osmosis
takes place:
 the molecules that are able to cross the membrane will
flow through it from the zones of high concentration of
the species to the ones of low concentration (diffusion).
 If the solvent is able to move, it will go from the dilute
side (high solvent concentration) into the concentrated
one (low solvent concentration)
The concentration of a species can be seen as a
pressure exerted on its molecules
The high solvent concentration side (low solute)
can be considered as high pressure.
The Osmosis will take place as long as the
pressures on both sides are non equal
When the solvent enters the low pressure side
(high solute), the solution volume increases,
leading to a rise in level, and therefore an
increase in hydrostatic pressure.
After a while, the sum of the concentration
pressure and the hydrostatic pressure on the
high solute side will equal the concentration
pressure on the low solute side, and osmosis
will stop.
We call this hydrostatic pressure that has to be
applied to stop osmosis the Osmotic Pressure
If one applies on the high solute concentration
side a pressure higher than the osmotic
pressure, the osmosis phenomenon can be
forced to go backwards. (Inverse Osmosis)
This can be used to purify water, pressing clean
water out of a dirty or contaminated solution.
The osmotic pressure of a solution against the pure
solvent is given by:

π  M R  T
Where p is the pressure measured in the units indicated by the value or the gas
constant R chosen, M is the molarity of the solution, and T is the temperature
in Kelvins
If one measures the pressure in atmospheres, the concentration in molar
and T in Kelvins, R is 8.21 x 10-2 L.atm.K-1.mol-1
If one measures the pressure in Pascals, the concentration in moles per m3
and T in kelvins, then R is 8.314 J.k-1.mol-1
 A solution is made up from a solid solute A, Mw = 85 g/mol,
and a liquid solvent B, Mw = 45 g/mol, density 0.85 g/ml,
Tf= 25°C, Tb = 70°C, kf = 2.0°C/molal and kb =
0.6°C/molal. The vapor pressure of B at 25°C is 35 mmHg.
140 g of A are dissolved in 2.5 liters of B, leading to a solution
of a density of 0.83 g/ml

Calculate
• The vapor pressure of the solution at 25°C
• The range of temperatures in which the solution is liquid
• The osmotic pressure of the solution at 300 K
  Lets fill up our data tables from the problem
statement

• We have 140 g of A, and therefore 140 g / 85 g/mol = 1.647 moles of A

• We have 2.5 liters of B, that is 2500 ml x 0.85 g/ml = 2125 g of B
• This also means that we have 2125 g / 45 g/mol = 47.222 moles of B
•The total weight of the solution is 140 g + 2125 g = 2265 g
•And its volume is 2265 g / 0.83 g/ml = 2728.91 or 2729 ml
• We have 140 g of A, and therefore 140 g / 85 g/mol = 1.647 moles of A
• We have 2.5 liters of B, that is 2500 ml x 0.85 g/ml = 2125 g of B
• This also means that we have 2125 g / 45 g/mol = 47.222 moles of B
•The total weight of the solution is 140 g + 2125 g = 2265 g
•And its volume is 2265 g / 0.83 g/ml = 2728.91 or 2729 ml

Volume weight
Sample 2729 ml (2.729 liters) 2265 g

Component Moles Weight

A 1.647 140 g
B 47.222 2125 g
Total 48.869 2265 g
 The solution vapor pressure is given as:
Psolution  Psolvent
0
 χ solvent Psolution  Psolvent
0
 ΔP  Psolvent
0
 Psolvent
0
 χ solute

We have to calculate c for both solvent and solute

n solvent 47.222 n solute 1.647
χ solvent    0.9663 χ solute    0.0337
n total 48.869 n total 48.869

The vapor pressure of the solution is

Psolution  Psolvent
0
 χ solvent  35mmHg  0.9663  33.82mmHg

Psolution  Psolvent
0
 Psolvent
0
 χ solute  35  35  0.0337  35  1.18  33.82mmHg
 The molality of the solution is
nA 1.647
m  1000  0.775molal
1kgsolvent 2125

•The decrease in melting point is DTf = kf.m = 2.0 x 0.775 = 1.55 °C

•The new melting point is 25 – 1.55 = 23.45°C
•The increase in boiling point is DTb = kb.m = 0.6 x 0.775 = 0.465 °C
•The new boiling point is 70 + 0.465 = 70.465
•The solution will be liquid between 23.45 and 70.465 °C
 The molarity of the solution is
nA 1.647
M  1000  0.6035
1litersolu tion 2729

•The osmotic pressure is therefore P = R.T.M = 0.0821 x 300 x 0.6035 = 1.49 atm
•The result is in atmospheres as we used R in units of L.Atm.mol-1.k-1
 If the weight of an unknown compound put in
solution in a known amount of solvent is
known, one can find its molecular weight from
the measurement of a colligative property
 Consider that we measure DTf. From that we
can get the molality m, and:
w solute(g)
n solute Mw solute(g/mol)
m  1000(g/kg)
1kg solvent Wsolvent(g)
w solute 1000
m
Mw solute  Wsolvent
w solute 1000
Mw solute 
m  Wsolvent
 Replacing the molality by its value from the DTf measurement

Wsolute(g) 1000(g/kg)
Mw solute(g/mole) 
DTf
 Wsolvent(g)
kf
Wsolute(g) 1000(g/kg)
Mw solute(g/mole)   kf
DTf  Wsolvent(g)

 Therefore, the complete calculation is

Wsolute(g) 1000(g/kg) k f (C.kg/mole)
Mw solute(g/mole)  
Wsolvent(g) ΔTf (C)

 However, do note that this result is valid only if the

compound is a non electrolyte!
 2 grams of sucrose are disssolved in 250 ml of
benzene (density 0.8765 g/ml, kf = 5.12 °C/molal, Tf
= 5.5°C). The melting point of the solution is 5.36°C.
What is the molecular weight of sucrose?

 The decrease in melting point is 5.5 -5.36 = 0.14°C

 The weight of benzene is 250 x 0.8765 = 219.125 g
 Wsolute(g) 1000(g/kg) k f
Mw solute(g/mole)  
Wsolvent(g) DTf

2 1000  5.12
Mw   333.795g/m ol
219.125  0.14

(real value: 342 g/mol)