Solutions of Solids in Liquids

COLLIGATIVE PROPERTIES

•depend on the concentration (no. of

particles) of solute molecules or ions in
solution but not on the chemical identity of
the solute
COLLIGATIVE PROPERTIES

1. Vapor Pressure lowering

2. Boiling point elevation
3. Freezing point depression
4. Osmotic pressure
Vapor pressure lowering
if: P1 = P1o (1 - X2)

P 1 = P 1 o - P 1 o X2
P 1 o - P 1 = P 1 o X2

then: P
∆ 1 = P 1
o - P
1
Vapor pressure
lowering P
∆ 1 = P1
o X
2
PHASE DIAGRAM FOR PURE WATER
Adding solute to water
 ∆Tf ∆Tb

Tfo Tbo

Tf Tb
 Boiling point elevation

ΔTb  m
ΔTb = kbm Kb H20 = 0.51
Kb Wsolute
 Tb 
M W solute x Kg solvent

ΔTb = Tb -Tbo
Freezing point depression

ΔTf  m
ΔTf = kfm Kf H20 = 1.86
Kf Wsolute
 Tf 
M W solute x Kg solvent

ΔTf = Tfo - Tf
Kb = ebullioscopic constant or
molal boiling point constant

Kf = cryoscopic constant or
molal freezing point constant
 Osmosis
• spontaneous process
• diffusion of water across a semi-permeable
membrane
• semi-permeable membrane allows passage of
solvent but not solute
 Osmosis
•movement of solvent from lower solute
concentration to higher solute concentration

• movement of solvent from higher solvent

concentration to lower solvent concentration
Osmosis
Osmotic Pressure
• Pressure required to stop osmosis

PV = nRT
if P = ∏ and n/V = M
then ∏ = MRT
∏ = mRT
Cryoscopic method:
∏ = mRT
ΔTf = kfm
Tf
m
Kf
Tf R T where
 R = 0.0821 L-atm/n-K
Kf
 SUMMARY

Non-electrolytes Electrolytes

∆P1 P1o X2 i P1o X2

ΔTb kbm i kbm
ΔTf Kf m i Kf m
∏ mRT i mRT

i = dissociation or Van’t Hoff factor

 Calculate the
Dissociation Value (i)

KCl is a 2-ion electrolyte dissociating 80% in a certain concentration.

Calculate its dissociation value (i).

80 K+ ion
80 Cl- ion
20 undissociated particles
180 particles represent 1.8 times as many particles as there were
before dissociation, i = 1.8
ZnCl2 is a 3-ion electrolyte dissociating 80% in a certain
concentration. Calculate its dissociation value (i).

80 Zn+ + ion
80 Cl- ion
80 Cl- ion
20 undissociated particles
260 particles represent 2.6 times as many particles as
there were before dissociation, i = 2.6
 Dissociation values (i)

Non-electrolytes 1.0

Electrolytes (2 –ion) 1.8

Electrolytes (3 –ion) 2.6

Electrolytes (4 –ion) 3.4

Electrolytes (5 –ion) 4.2

 Freezing point depression using Liso (for
electrolytes)

ΔTf = ikfm (Van’t Hoff Eq.)

Liso = ikf
ΔTf = Liso m (modified Van’t Hoff Eq.)

Liso = based on the valence of the compound

= determined by the ionization properties of the solute
 Dissociation vs. Ionization
Dissociation
= separation of charged particles which already exist in a
compound
ex. NaCl + H20 = Na+ + Cl-

Ionization
= produces new charged particles
ex. H20 + H20 = H30+ + OH-
 Approximate Liso value

Compound type by valence Liso value

Non-electrolyte 1.86

Weak electrolyte 2.0

Di-divalent electrolyte
2.0
(Divalent cation -divalent anion)
Uni-Univalent electrolyte 3.4
Uni-divalent electrolyte 4.3
Di-univalent electrolyte 4.8
Problems:
8. How many grams of urea (N2H4CO) must be added to 4000.0 g of water to make
the solution boil at 100.320C?

9. What is the molecular weight of a non-electrolyte substance if a solution of 3.00 g

in 200.0 g of benzene freezes at 4.980C? (Tf of benzene = 5.50C; Kf = 5.12)

10. How many molecules of sucrose must be added to 10.0 g of water at 10.000C if an
osmotic pressure of 0.80 atm is to be established?

11. The freezing point of a 0.28 m aqueous solution of Sodium sulfate is -1.360C.
What is (a) i (b) osmotic pressure at 00C (c) boiling point and (d) vapor pressure of the
solution at 20.00C? V.P. of pure water at 20.00C is 17.53 mm? (Express final answer in
5 significant figures)
Problems:
12. You are examining forensics data for a court case and need to identify an
analgesic (pain killer). It could be either acetylsalicylic acid (aspirin), ibuprofen (advil)
or acetaminophen (Tylenol). A mixture of the unknown is prepared by mixing 10.0 g
of unknown and dilution to 250. mL with ethanol. The density of this solution is
0.800 g/mL. Identify the unknown based upon the following:
a. The boiling point of this mixture is 78.80C.
b. The osmotic pressure of this mixture is 4.80 x 105 Pa at 25.00C.

Additional data:
acetylsalicylic acid (aspirin) = C9H8O4
ibuprofen (advil) = C13H18O2
acetaminophen (Tylenol) = C8H9NO2
Boiling point of ethanol = 78.50C
Kb of ethanol = 1.22