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Colligative Properties:

Colligative property: physical properties of solutions that are affected by the number
(but not the identity) of dissolved solute particles.
• Include vapor pressure lowering, boiling point elevation, freezing point
depression & osmotic pressure. (based on molal conc.)

Electrolytes vs. nonelectrolytes:


a) Electrolytes – form ions in solution
(conduct electricity)

(1) Ex. NaCl (s)  Na+ (aq) + Cl- (aq)


1 Mole 1 mole 1 mole

*(2) Note: 1 mol NaCl yields 2 moles of ions

b) Nonelectrolytes - do not ionize (don’t conduct electricity)

(1) Ex. C6H12O6 (s)  C6H12O6 (aq)


1 mole 1 mole

(2) Note: 1 mole C6H12O6 yields 1 mole

*NaCl has greater effect on colligative properties.

Examples of colligative properties and how they work:

• Vapor pressure decrease

1. Vapor pressure can be thought of as a measure of the tendency of molecules


to escape the liquid phase and enter the gas phase.
2. Addition of a nonvolatile substance (substance that has little tendency to
become a gas under existing conditions), lowers the concentrations of water
molecules at the surface of the liquid which lowers the tendency of the water
molecules to leave the liquid phase.
3. Vapor-pressure is lowered by the addition of nonvolatile substances

The French chemist Francois Raoult discovered the law that mathematically describes
the vapor pressure lowering phenomenon. Raoult's law is given in :
Psolution= χsolvent Psolvent

Raoult's law states that the vapor pressure of a solution, Psolution, equals the mole
fraction of the solvent, χsolvent, multiplied by the vapor pressure of the pure solvent,
Psolvent.
• Boiling point elevation:

○ As you increase the concentration of a solution, the boiling point of the solution
increases.

○ The reason for this is that adding solute decreases the vapor pressure of a
solution because there are fewer molecules at the surface of the solution that
can vaporize. Because liquids boil when their vapor pressure is equal to the
ambient atmospheric pressure, you need to heat them more to make them boil.

○ The relationship between concentration and boiling point is described by the


equation:

∆Tb = Kbm
Where:
 ∆Tb is the change in boiling point
 Kb is the ebullioscopic constant (0.520 C/m for water)
 m is the effective molality of the solute

○ “Effective molality” refers to the molality of particles in the solution.

• For covalent compounds (non-electrolytes), the effective molality is the


same as the regular molality because the molecules don’t break into
smaller pieces when you put them in water.
• For example, if you have a 0.75 m solution of CS2, the effective molality is 0.75
m.
 For ionic compounds (electrolytes), the effective molality is equal to the
molality times the number of ions in the compound.
• For example, if you have a 0.75 m solution of NaCl, the effective molality is
1.50 m (0.75 x 2)

○ Sample problems:
• What is the boiling point of a 1.75 m solution of formaldehyde (H2CO) in
analine? 190.60 C
• What is the boiling point of a 1.75 m solution of Ca3(PO4)2? 104.550 C
• Freezing point depression:

○ Solutions melt at lower temperatures than pure liquids because the solute
molecules disturb the intermolecular forces between the solvent molecules. As
a result, less energy is needed to break up the solid.

○ The relationship between concentration and melting point is determined by the


equation:
∆Tf = Kfm
Where:
 ∆Tf is the change in freezing point
 Kf is the cryoscopic constant (1.860 C/m for water)
 m is the effective molality of the solute

○ The rules for determining effective molality are the same as for boiling point.
The only thing different is the constant used.
 Example: What is the melting point of a 1.75 m solution of NaCl? -6.510
C

Colligative property data for some common solvents

normal normal
solvent freezing kf boiling kb(°C/m)
point (°C/ point
(°C) m) (°C)
water 0.00 -1.86 100.00 0.52
aniline -6.1 -5.87 184.4 3.52
phenol 40.9 -7.27 181.8 3.56
camphor 178.40 -40.00
benzene, 5.48 -5.12 80.15 2.53
C6H6
ether -116.3 -1.79 34.42 2.02

• Osmotic pressure increase

○ Osmosis – diffusion of solvent particles across semipermeable membrane


(from higher to lower concentration).
○ Osmotic pressure is the force with which a pure solvent moves across a semi-
permeable barrier into a container that holds a solution.
○ Membrane has tiny pores that allows water to pass through but not sucrose
(solute).
○ When sucrose is added, water & sucrose contact the membrane on the
solution side; only water contacts the membrane on the solvent side.
○ More water moves from solvent side to solution side.
○ This occurs because solvents tend to diffuse across barriers in ways that will
decrease the difference in concentration. The bigger the difference in
concentration (because of high solute concentration), the stronger the force of
osmosis.