Colligative

Properties
Nathaniel P. Dugos
Adamson University
Manila, Philippines
Colligative properties

Properties determined by the number of

particles in solution rather than the type
of particles.

Vapor pressure lowering

Freezing point depression
Boiling point elevation
Osmotic pressure
 How Vapor Pressure Lowering
Occurs
 Solute particles take up space in a
solution.
 Solute particles on surface decrease
number of solvent particles on the
surface.
 Less solvent particles can evaporate
which lowers the vapor pressure of
a liquid.
 Vapor Pressures of Pure Water and a Water Solution
The vapor pressure of water over pure water is greater than the vapor
pressure of water over an aqueous solution containing a nonvolatile
solute.

Solute particles take up

surface area and lower
the vapor pressure
Vapor Pressure Lowering
Let component A be the solvent and B the solute.
solute B is nonvolatile

Applying Raoult’s Law: PA  X A P *

A

where: PA= vapor pressure of the solvent in solution

= vapor pressure of the solution
*
PA = vapor pressure of the pure solvent
XA = mole fraction of the solvent
The lowering in vapor pressure, P

P  P  PA*
A

 P P XA
*
A
*
A

 (1  X A ) P *
A

P  X B P *
A

where: XB = mole fraction of solute

Sample Problems (Vapor Pressure Lowering)

1. What mass of urea, CON2H4, must be added to

450 g water to get a solution with a vapor pressure
of 29.3 mmHg? The vapor pressure of pure water
is 31.8 mmHg at this temperature.
Sample Problems (Vapor Pressure
Lowering

2. The vapor pressure of 2-propanol is 50.00 kPa

at 338.8oC, but fell to 49.62 kPa when 8.69 g of
an involatile organic compound was dissolved
in 250-g of 2-propanol. Calculate the molar
mass of the compound.
Boiling Point Elevation
When a non volatile solute is added to
solvent:
• Vapor pressure of solvent is lowered

• solution formed must be heated to higher

temperature than boiling point of pure
solvent to reach a vapor pressure of 1 atm.

• This means that non volatile solute elevates

the boiling point of the solvent which we call
boiling point elevation
Boiling Point Elevation
 RT *2 
T   X B
  vap H 
 

mB
XB   mB M A (for dilute solutions)
1 / M A  mB

where MA is the molar mass of the solvent and

mB the molality of the solute in mol/kg

Boiling Point Elevation
 RTb*2 M A 
T    mB
  H 
 vap 

Tb  K b m for dilute solutions

 RTb *2 M A 
where Kb  
  H 
 vap 

K b = boiling point constant or ebullioscopic

constant of the solvent
Freezing Point Depression

Addition of a nonvolatile solute to a solution

lowers the freezing point of the solution
relative to the pure solvent.
Freezing Point Depression
T f  K f m (for dilute solutions)

 RT f M A 
*2

where K f   
  fus H 
 
K f = molal freezing point depression
constant or cryoscopic constant
What is the value of the freezing point constant
for water? The enthalpy of fusion at 273.15 K is
6.00 kJ mol-1

The molal freezing point depression constant of

benzene is 5.12. A 0.450% solution of
monoclinic sulfur in benzene freezes 0.088 K
below the freezing point of pure benzene. Find
the molecular formula of the sulfur in benzene.
Osmosis
There are many times in nature when a solvent will
pass spontaneously through a semipermeable
membrane, which is a membrane permeable to
solvent, but not solute

The osmotic pressure, Π, is the pressure that

must be applied to stop the influx of solvent
Osmosis
Examples:

(a) the transport of fluids through living cell

membranes
(b) basis of osmometry, the determination of
molecular mass by measurement of osmotic
pressure
Osmosis
Eventually the pressure difference between the arms stops osmosis.
Osmosis
To treat osmosis thermochemically, we note
that at equilibrium, the chemical potential on
each side of the membrane must be equal

Equilibrium is established when the hydrostatic

pressure of the solution in the column is equal
to the osmotic pressure

Pure solvent side :  *A ( p ) at pressure p

Solution side : x A  1 so  *A is lowered by solute to  A
However  A is now increased by greater pressure p  
 *A ( p)   A ( x A , p  )
account for the presence of solute
 A ( x A , p  )   *A ( p  )  RT ln x A
take the effect of pressure into account
p 

 *A ( p  )   *A ( p)   V dp
p
m

where Vmis the molar volume of pure solvent A

combining equations, we have
p 

 RT ln x A   V dp
p
m

Dilute solutions : ln x A replaced by ln(1  x A )   xB and Vm is constant

RTxB   Vm
 RTx B   Vm
nB
When the solute is dilute, xB  . Because n AVm  V ,
nA
total volume of the solvent, the equation simplifies to

  [ B]RT
nB
where [ B ]  is the molar concentration of the solute
V
A solution of polystyrene in benzene contains
10 g/L. The equilibrium height of the column of
solution (density 0.88 g cm-3) in the osmometer
corrected for capillary rise is 11.6 cm at 25oC.
What is the molar mass of polystyrene, assuming
the solution is ideal.

The osmotic pressure of an aqueous solution

at 300 K is 120 kPa. Calculate the freezing
point of the solution.
Osmometry

Osmotic pressure is easily measured, and is quite large.

Osmometry can be applied for the determination of
molecular weights of large molecules (proteins, synthetic
polymers), which dissolve to produce less than ideal
solutions. The Van’t Hoff equation can be rewritten in
virial form:

Π= [B] RT {1 + B [B] + ...}

where B is the empirically determined osmotic virial

coefficient
 Consider the example of poly (vinyl chloride) PVC, in
cyclohexanone at 298 K

Pressures are expressed in terms of heights of solution,

ρ=0.980 g cm-3 in balance with the osmotic pressure

c (g L-1) 1.00 2.00 4.00 7.00 9.00

h (cm) 0.28 0.71 2.01 5.10 8.00

Use Π = [B] RT {1 + B [B] + …} with [B] = c/M, where c

is the mass concentration and M is the molar mass. The
osmotic pressure is related to the hydrostatic pressure by
Π = ρgh, where g = 9.81 m s-2. Then:
 h RT  Bc  RT  RTB 
 1     c
2 
c gM  M  gM  gM 

Plot h/ c vs. c to find M, expecting a straight line with

intercept RT/ ρgM at c = 0.

Data set:
c(g L-1) 1.00 2.00 4.00 7.00 9.00
h/c(cm g-1 L) 0.28 0.36 0.53 0.729 0.889
The data give an
intercept of 0.21 g/mL
The data give an intercept of 0.21 cm g-1 L, which is equal to
RT/ ρgM

Thus:
RT 1
M  
g 0.21 cmg 1 L


 8.314 JK 1 1

mol  (298K )

1
3 2
(980kgm )  (9.81ms ) 2.1103 m 4 kg 1
 1.2 10 2 kgmol 1

where we have used 1 kg m2 s-2=1J